WO2019073530A1 - Nanocarbon separation device, nanocarbon separation method, nanocarbon recovery method - Google Patents

Nanocarbon separation device, nanocarbon separation method, nanocarbon recovery method Download PDF

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WO2019073530A1
WO2019073530A1 PCT/JP2017/036717 JP2017036717W WO2019073530A1 WO 2019073530 A1 WO2019073530 A1 WO 2019073530A1 JP 2017036717 W JP2017036717 W JP 2017036717W WO 2019073530 A1 WO2019073530 A1 WO 2019073530A1
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Prior art keywords
nanocarbon
electrode
walled carbon
separation
porous structure
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PCT/JP2017/036717
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French (fr)
Japanese (ja)
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和紀 井原
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日本電気株式会社
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Priority to US16/754,048 priority Critical patent/US11383983B2/en
Priority to PCT/JP2017/036717 priority patent/WO2019073530A1/en
Priority to JP2019547822A priority patent/JP6939891B2/en
Publication of WO2019073530A1 publication Critical patent/WO2019073530A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/172—Sorting
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D57/00—Separation, other than separation of solids, not fully covered by a single other group or subclass, e.g. B03C
    • B01D57/02—Separation, other than separation of solids, not fully covered by a single other group or subclass, e.g. B03C by electrophoresis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a nanocarbon separation device, a nanocarbon separation method, and a nanocarbon recovery method.
  • Single-walled carbon nanotubes have high electron mobility, and their application to various fields is expected from their mechanical properties, electrical properties, chemical properties, and the like.
  • Single-walled carbon nanotubes are synthesized as a mixture containing materials with different properties of semiconductivity and metallicity in a ratio of 2: 1. Therefore, for industrial application, high purity and rapidity per property are achieved. Need to do separation.
  • a method of separating a mixture of single-walled carbon nanotubes for example, a dispersion solution of a nanocarbon material dispersed in nanocarbon micelles having different charges, and a holding solution having a different specific gravity from the nanocarbon material, The step of stacking and introducing in a predetermined direction in the electrophoresis tank, and applying a DC voltage in series to the dispersed solution and the holding solution which are stacked and introduced, two or more of the nanocarbon micelle groups And a step of separating into a group of nano carbon micelles of (1), (2).
  • a DC voltage is applied to the single-walled carbon nanotube-containing micelle dispersion solution in which single-walled carbon nanotubes are dispersed in a non-ionic surfactant solution in a separation tank vertically disposed, and each micelle as a whole
  • a method of separating single-walled carbon nanotubes comprising the step of separating into at least two layers, wherein a direct current voltage is applied by the cathode disposed at the top of the separation vessel and the anode disposed at the bottom, and the direction of the electric field
  • a method of separating single-walled carbon nanotubes in which the direction is parallel to the direction of gravity and points upward (see, for example, Patent Document 2) .
  • Patent No. 5541283 gazette Patent No. 5717233 gazette
  • An object of the present invention is to provide a nanocarbon separation device, a nanocarbon separation method, and a nanocarbon recovery method, in which the time required for separation is reduced in the separation of a mixture of nanocarbons.
  • a nanocarbon separation apparatus comprises a separation vessel for containing a dispersion containing nanocarbon, a first electrode provided in the upper part in the separation vessel, and a second part provided in the lower part in the separation vessel. And a porous structure provided between the first electrode and the second electrode in the separation tank.
  • the method for separating nanocarbons according to the present invention is a method for separating nanocarbons using the apparatus for separating nanocarbons according to the present invention, comprising the steps of: injecting a dispersion containing nanocarbon into the separation tank; and the first electrode And applying a DC voltage to the second electrode to separate the metal nanocarbon and the semiconductor nanocarbon contained in the dispersion.
  • the method for recovering nano carbon of the present invention is a method for recovering nano carbon using the nano carbon separation device of the present invention, wherein the porous structure is treated with a metal after the separation operation by the nano carbon separation device is completed.
  • the region is divided into a region A containing a large amount of nanocarbon and a region B containing a large amount of semiconductor nanocarbon, the metal nanocarbon is recovered from the region A, and the semiconductor nanocarbon is collected from the region B.
  • the time required for the separation can be shortened.
  • FIG. 1 is a schematic view showing a nanocarbon separation device of the present embodiment.
  • the nanocarbon separation apparatus 10 includes a separation tank (electrophoresis tank) 11, a first electrode 12 provided in the upper part in the separation tank 11, and a second electrode provided in the lower part in the separation tank 11. And a porous structure 14 provided between the first electrode 12 and the second electrode 13 in the separation tank 11 so as to extend along the height direction of the separation tank 11; And.
  • the porous structure 14 is made of a sponge which is a porous soft body having numerous fine holes therein.
  • the first electrode 12 is located in the upper side in the height direction in the separation tank 11 (in the area above the half of the height in the separation tank 11, on the opposite side to the inner bottom surface 11 a of the separation tank 11) Area) is arranged.
  • the second electrode 13 is located in the lower part in the height direction in the separation tank 11 (in the area below the half of the height in the separation tank 11, the area on the inner bottom surface 11a side of the separation tank 11) It is arranged.
  • the first electrode 12 is a cathode
  • the second electrode 13 is an anode. In this case, when a DC voltage is applied to the first electrode 12 and the second electrode 13, the direction of the electric field is directed upward from below the separation tank 11.
  • the separation tank 11 has a space capable of accommodating a dispersion liquid containing nanocarbon (hereinafter, referred to as “nanocarbon dispersion liquid”) 30.
  • the separation tank 11 is for separating nanocarbon dispersed in the contained nanocarbon dispersion liquid 30 by electrophoresis.
  • the shape and size of the separation tank 11 are not particularly limited as long as the separation tank 11 can accommodate the nanocarbon dispersion liquid 30.
  • the separation tank 11 is a container having a hollow tube. The lower end of the separation tank 11 is closed and is the bottom of the container.
  • the material of the separation tank 11 is not particularly limited as long as it is stable to the nanocarbon dispersion liquid 30 and is an insulating material.
  • a material of the separation tank 11 glass, quartz, an acrylic resin etc. are mentioned, for example.
  • the first electrode 12 and the second electrode 13 can be used for electrophoresis, and are not particularly limited as long as they are stable with respect to the nanocarbon dispersion liquid 30.
  • Examples of the first electrode 12 and the second electrode 13 include a platinum electrode and the like.
  • the structure of the first electrode 12 and the second electrode 13 is not particularly limited, and may be appropriately selected according to the shape and size of the area partitioned by the porous structure 14 in the separation tank 11.
  • the structure of the first electrode 12 is not particularly limited as long as it is disposed on the top of the porous structure 14 and disposed so as to extend over the entire top end of the porous structure 14 in the separation tank 11.
  • the structure of the second electrode 13 is particularly limited as long as it is disposed in the lower part of the porous structure 14 and disposed so as to extend over the entire lower end of the porous structure 14 in the separation tank 11. I will not.
  • Examples of the structure of the first electrode 12 and the second electrode 13 include, in a plan view of the separation tank 11, an annular shape, a disk shape, a rod shape, and the like. Moreover, as a structure of the 1st electrode 12 and the 2nd electrode 13, the porous-plate shape in which many micropores were provided uniformly is mentioned.
  • the sponge that forms the porous structure 14 is not particularly limited.
  • the material of the sponge is not particularly limited as long as it is stable to the nanocarbon dispersion liquid 30 and is an insulating material.
  • the sponge is a porous body in which fine pores are continuously connected inside and innumerably opened. Examples of the sponge include those made of natural sponge, and artificial sponges made of synthetic resin. Moreover, as a material of a sponge, the porous material which can hold
  • the porous material for example, urethane; synthetic sponges using foamed polyethylene, polyethylene, ethylene propylene rubber, chloroprene rubber, natural rubber, melamine resin etc .; natural sponge produced by sea surface organisms represented by Mok yokaimen; pumice stone Etc.
  • the urethane foam water absorption sponge (The such example; TRUSCO NAKAYAMA TRUSCO water absorption sponge) which is 98.5% of the porosity can be used. Therefore, the inside of the separation tank 11 is divided into a large number of regions by the porous structure 14 made of a sponge.
  • the size (height, outer diameter, volume, etc.) of the porous structure 14 is not particularly limited, and is appropriately adjusted according to the amount of the nanocarbon dispersion liquid 30 to be held by the porous structure 14.
  • the porosity (porosity) in the porous structure 14 is any porosity as long as the nanocarbon micelles can pass through and pores are continuously connected to form a potential gradient between the upper and lower electrodes. It is very good.
  • the porosity (porosity) of the porous structure 14 is preferably 80% to 99.9%, and more preferably 90% to 99%.
  • the porous structure 14 when the porosity in the porous structure 14 is 80% or more, the pores communicate with each other throughout the porous structure 14, and the dispersion of nanocarbons using the nanocarbon separation device 10 In the separation of the liquid 30, the porous structure 14 does not prevent the movement of the metallic nanocarbon and the semiconductive nanocarbon contained in the nanocarbon dispersion liquid 30. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
  • the porosity of the porous structure 14 is a ratio of the pores of the porous structure 14 to the total volume of the porous structure 14.
  • the porosity of the porous structure 14 is represented by the following formula (1). a1 / A1 ⁇ 100 (1) That is, the porosity of the porous structure 14 is expressed as a percentage of the ratio of the total area al of the pores of the porous structure 14 to the total area Al of the porous structure 14 including the pores.
  • the apparent specific gravity d1 of the porous structure 14 including pores and the true specific gravity D1 of the porous structure 14 including are determined, and those specific gravity From the above, a method of calculating the porosity of the porous structure 14 can be mentioned.
  • the porosity of the porous structure 14 is calculated based on the following equation (2). (D1-d1) / D1 ⁇ 100 (2)
  • the size of the pores of the porous structure 14, that is, the inner diameter of the pores is preferably 40 nm or more, more preferably 100 nm or more, and still more preferably more than 200 nm.
  • the inner diameter of the pores is preferably 1 cm or less, more preferably 1 mm or less.
  • the porous structure 14 is included in the nanocarbon dispersion 30 in the separation of the nanocarbon dispersion 30 using the nanocarbon separation device 10 It does not prevent the movement of metallic nanocarbon and semiconducting nanocarbon. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
  • the shape of the pores of the porous structure 14 is indeterminate, and for example, it has a spherical shape, a spheroid shape, or the like. Therefore, the inner diameter of the pores of the porous structure 14 means the diameter of the sphere when the pores are spherical, the major diameter of the spheroid when the pores are spheroid, and the pores In the case of shapes other than spherical and spheroidal, it is the length of the longest part of the shape.
  • a method of determining the size of the pores of the porous structure 14 for example, a method of observing the porous structure 14 with an optical microscope or a scanning electron microscope and measuring the size of the pores from the microscopic image, etc. Can be mentioned.
  • the porous structure 14 is transparent, milky white and translucent (white in which the back is seen through), in order to make it easy to confirm the separation state of the metallic nanocarbon and the semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30. It is preferable that it is milky white (the back is opaque and it is white which is not transparent).
  • the dispersion 30 of the nanocarbon having a large content of the metallic nanocarbon turns black, and the dispersion 30 of the nanocarbon having a large content of the semiconducting nanocarbon It becomes blue. Therefore, it is preferable to visually confirm the separation state of the metallic nanocarbon and the semiconducting nanocarbon on the background of the color of the porous structure 14.
  • the porous structure 14 preferably extends in the separation tank 11 in the region between the first electrode 12 and the second electrode 13 over substantially the entire height direction of the region.
  • the outer shape of the porous structure 14 is preferably similar to the shape of the region between the first electrode 12 and the second electrode 13 in the separation tank 11.
  • the nanocarbon separation apparatus 10 of the present embodiment may include an injection port (not shown) for injecting the dispersion liquid 30 of nanocarbon into the separation tank 11.
  • the inlet is provided at the upper side in the height direction in the separation tank 11 (in the area above the half of the height in the separation tank 11, the area on the opposite side to the inner bottom surface 11a of the separation tank 11) It may be When the upper end of the separation tank 11 is an opening 11 b, the opening 11 b may be an injection port for injecting the dispersion 30 of nanocarbon into the separation tank 11.
  • nanocarbon separation device 10 of this embodiment is not limited to this.
  • the first electrode 12 may be an anode
  • the second electrode 13 may be a cathode.
  • a porous structure provided so as to extend along the height direction of the separation tank 11 between the first electrode 12 and the second electrode 13
  • the step of separating metal-type nanocarbon and semiconductor-type nanocarbon contained in dispersion liquid 30 of nanocarbon for example, implementing the separation method of nanocarbon described later by providing 14.
  • the occurrence of horizontal flow in the nanocarbon dispersion liquid 30 can be suppressed. Therefore, metallic nanocarbon and semiconducting nanocarbon can be separated rapidly. Therefore, metal nanocarbon and semiconductor nanocarbon with high purity can be obtained.
  • FIG. 3 is a flowchart showing the method for separating nanocarbons of the present embodiment.
  • a step of injecting the dispersion 30 of nanocarbon into the separation tank 11 (hereinafter referred to as “injection step”), and direct current to the first electrode 12 and the second electrode 13. And applying a voltage to separate the metallic nanocarbon and the semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 (hereinafter, referred to as “separation step”).
  • the nanocarbons are mainly composed of carbon such as single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nano-swipe, graphene, fullerene, etc. It means carbon material.
  • carbon material such as carbon material.
  • single-walled carbon nanotubes are divided into two different properties of metallic type and semiconductive type depending on the diameter and winding method of the tube.
  • metallic single-walled carbon nanotubes having metallic properties and semiconducting single-walled carbon nanotubes having semiconducting properties are statistically in a ratio of 1: 2
  • a mixture of single-walled carbon nanotubes is obtained.
  • the mixture of single-walled carbon nanotubes is not particularly limited as long as it contains metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
  • the single-walled carbon nanotube in the present embodiment may be a single-walled carbon nanotube alone, or may be modified with a single-walled carbon nanotube in which a part of carbon is substituted with an arbitrary functional group, or an arbitrary functional group. It may be a single-walled carbon nanotube.
  • a single-walled carbon nanotube dispersion is prepared in which a mixture of single-walled carbon nanotubes is dispersed in a dispersion medium together with a surfactant.
  • the dispersion medium is not particularly limited as long as the mixture of single-walled carbon nanotubes can be dispersed.
  • examples of the dispersion medium include water, heavy water, an organic solvent, an ionic liquid and the like.
  • water or heavy water is preferably used because single-walled carbon nanotubes do not deteriorate.
  • nonionic surfactant nonionic surfactant, cationic surfactant, anionic surfactant etc.
  • cationic surfactant cationic surfactant
  • anionic surfactant it is preferable to use a nonionic surfactant.
  • nonionic surfactant a nonionic surfactant having a non-ionizing hydrophilic site and a hydrophobic site such as an alkyl chain is used.
  • nonionic surfactants include nonionic surfactants having a polyethylene glycol structure represented by polyoxyethylene alkyl ether.
  • polyoxyethylene alkyl ether represented by the following formula (1) is suitably used.
  • polyoxyethylene alkyl ether represented by the above formula (1) examples include polyoxyethylene (23) lauryl ether (trade name: Brij L23, manufactured by Sigma Aldrich), polyoxyethylene (20) cetyl ether (trade name) : Brij C20, manufactured by Sigma Aldrich), polyoxyethylene (20) stearyl ether (trade name: Brij S20, manufactured by Sigma Aldrich), polyoxyethylene (20) oleyl ether (trade name: Brij O20, manufactured by Sigma Aldrich) And polyoxyethylene (100) stearyl ether (trade name: Brij S100, manufactured by Sigma Aldrich Co.) and the like.
  • polyoxyethylene sorbitan monostearate molecular formula: C 64 H 126 O 26 , trade name: Tween 60, manufactured by Sigma Aldrich
  • polyoxyethylene sorbitan trioleate molecular formula: C 24 H 44 O 6 , trade name: Tween 85, manufactured by Sigma Aldrich
  • Triton X-100 Sigma-Aldrich
  • polyoxyethylene (40) isooctylphenyl ether molecular formula: C 8 H 17 C 6 H 40 (CH 2 CH 20 ) 40 H, trade name: Triton X-405, manufactured by Sigma-Aldrich
  • Poloxamer molecular formula: C 5 H 10 O 2 , trade name: Pluronic, manufactured by Sigma Aldrich, polyvinyl pyrrolidone (molecular formula: C 5 H 10 O 2 , trade name
  • the content of the nonionic surfactant in the single-walled carbon nanotube dispersion is preferably 0.1 wt% or more and 5 wt% or less, and more preferably 0.5 wt% or more and 2 wt% or less. If the content of the nonionic surfactant is 5 wt% or less, the viscosity of the single-walled carbon nanotube dispersion does not become too high, and the metal type contained in the single-walled carbon nanotube dispersion easily by electrophoresis. Single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes can be separated.
  • the content of single-walled carbon nanotubes in the single-walled carbon nanotube dispersion liquid is preferably 1 ⁇ g / mL or more and 100 ⁇ g / mL or less, and more preferably 5 ⁇ g / mL or more and 40 ⁇ g / mL or less. If the content of single-walled carbon nanotubes is in the above range, metal single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion can be easily separated by electrophoresis.
  • the method of preparing the single-walled carbon nanotube dispersion is not particularly limited, and known methods may be used. For example, there is a method in which a mixture of a single-walled carbon nanotube mixture and a dispersion medium containing a surfactant is subjected to ultrasonication to disperse the single-walled carbon nanotube mixture in the dispersion medium. By this ultrasonic treatment, the aggregated metal single-walled carbon nanotubes and the semiconductor single-walled carbon nanotubes are sufficiently separated, and the single-walled carbon nanotube dispersion liquid contains metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes as a dispersion medium. The multi-walled carbon nanotubes become uniformly dispersed.
  • metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes can be easily separated by the electrophoresis method described later.
  • metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes not dispersed by ultrasonication are separated and removed by ultracentrifugation.
  • the single-walled carbon nanotube dispersion prepared as described above is injected into the separation tank 11.
  • the single-walled carbon nanotube dispersion liquid infiltrates the porous structure 14 in the separation tank 11.
  • the first electrode 12 and the second electrode 13 are in contact with the single-walled carbon nanotube dispersion liquid.
  • the first electrode 202 and the second electrode 203 are immersed in the single-walled carbon nanotube dispersion liquid.
  • the first electrode 12 and the second electrode 13 do not have to be in contact with the porous structure 14.
  • metallic single-walled carbon nanotubes and semiconductive single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion liquid are separated by electrophoresis.
  • An electric field is formed in the separation tank 11 by applying a DC voltage to the first electrode 12 and the second electrode 13 for a predetermined time (for example, 1 hour to 24 hours). Specifically, the electric field is formed such that the direction of the electric field is from the bottom to the top of the separation tank 11.
  • a mixture of single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion is a metallic single-walled carbon nanotube and a semiconducting single-walled carbon nanotube by the electric field generated by the electric field and the charge of the single-walled carbon nanotube. It is separated.
  • the metallic single-walled carbon nanotube has a positive charge
  • the semiconducting single-walled carbon nanotube has an extremely weak negative charge
  • the metallic single-walled carbon nanotube is the first electrode 12 among the mixture of single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion. It moves to the (cathode) side, and the semiconductor single-walled carbon nanotube moves to the second electrode 13 (anode) side.
  • the single-walled carbon nanotube dispersion has a relatively semiconductive-type single-walled dispersion liquid phase (hereinafter referred to as “dispersed liquid phase A”) having a relatively high content of metallic single-walled carbon nanotubes.
  • a dispersed liquid phase (hereinafter referred to as “dispersed liquid phase B”) having a large content of carbon nanotubes, and formed between the dispersed liquid phase A and the dispersed liquid phase B, the metal single-walled carbon nanotubes and the semiconductor are relatively formed.
  • Phase separation into three phases with a dispersion liquid phase (hereinafter referred to as “dispersion liquid phase C”) having a low content of single-walled carbon nanotubes.
  • the region A containing a large amount of metallic single-walled carbon nanotubes that is, a region containing the dispersed liquid phase A is formed.
  • a region B containing a large amount of semiconductor single-walled carbon nanotubes that is, a region containing the dispersed liquid phase B is formed.
  • the direct current voltage applied to the first electrode 12 and the second electrode 13 is not particularly limited, and the distance between the first electrode 12 and the second electrode 13 or single-walled carbon in the single-walled carbon nanotube dispersion liquid It is suitably adjusted according to the content of the mixture of nanotubes and the like.
  • the DC voltage applied to the first electrode 12 and the second electrode 13 is an arbitrary value between 0 V and 1000 V or less. Do.
  • the DC voltage applied to the first electrode 12 and the second electrode 13 is 15 V or more and 450 V or less Is preferable, and more preferably 30 V or more and 300 V or less. If the DC voltage applied to the first electrode 12 and the second electrode 13 is 15 V or more, a pH gradient of the single-walled carbon nanotube dispersion liquid is formed in the separation tank 11, and the single-walled carbon nanotube dispersion liquid Can separate the metallic single-walled carbon nanotubes and the semiconducting single-walled carbon nanotubes from each other. On the other hand, if the DC voltage applied to the first electrode 12 and the second electrode 13 is 450 V or less, the influence of the electrolysis of water or heavy water can be suppressed.
  • the electric field between the first electrode 12 and the second electrode 13 is 0.5 V / cm or more and 15 V / cm or less Is preferable, and more preferably 1 V / cm or more and 10 V / cm or less. If the electric field between the first electrode 12 and the second electrode 13 is 0.5 V / cm or more, a pH gradient of the single-walled carbon nanotube dispersion liquid is formed in the separation tank 11 to obtain single-walled carbon The metallic single-walled carbon nanotubes and the semiconducting single-walled carbon nanotubes contained in the nanotube dispersion liquid can be separated. On the other hand, if the electric field between the first electrode 12 and the second electrode 13 is 15 V / cm or less, the influence of the electrolysis of water or heavy water can be suppressed.
  • the porous structure 14 comprised from sponge is provided in the separation tank 11, and the inside of the separation tank 11 is divided into many area
  • the region A including the dispersion liquid phase A is rapidly formed in the region on the first electrode 12 side in the porous structure 14, and the porous structure A region B containing the dispersion liquid phase B can be formed in the region on the second electrode 13 side in 14, and the single-walled carbon nanotube dispersion liquid can be phase-separated into the dispersion liquid phase A and the dispersion liquid phase B.
  • separation is performed by providing the porous structure 14 made of a sponge between the first electrode 12 and the second electrode 13.
  • the porous structure 14 made of a sponge between the first electrode 12 and the second electrode 13.
  • it can suppress that the flow of a horizontal direction arises in a single-walled carbon nanotube dispersion liquid.
  • metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes can be separated rapidly.
  • metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes with high purity can be obtained.
  • the case of separating a mixture of single-walled carbon nanotubes into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes has been exemplified.
  • the separation method is not limited to this.
  • the method of separating nanocarbons of the present embodiment for example, after separating into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes in the separation tank 11, only single-walled carbon nanotubes having desired properties are recovered.
  • the method may be performed as a method of purifying single-walled carbon nanotubes.
  • the porous structure 14 is replaced by metal single-walled carbon nanotubes. It is divided into a region A containing a large amount and a region B containing a large amount of semiconducting single-walled carbon nanotubes, metal single-walled carbon nanotubes are recovered from the region A, and semiconducting single-walled carbon nanotubes are collected from the region B.
  • the recovery method is not particularly limited, and any method may be used as long as the dispersion liquid phase A and the dispersion liquid phase B do not diffuse and mix.
  • the nanocarbon recovery method of the present embodiment for example, the following two methods are used as the recovery method.
  • the method of using the cutting blade 50 is mentioned, for example.
  • the porous structure 14 is cut up and down in the height direction by the cutting blade 50 while a direct current voltage is applied to the first electrode 12 and the second electrode 13 so that the porous structure is formed.
  • the object 14 is divided into a region A containing many metallic single-walled carbon nanotubes and a region B containing many semiconducting single-walled carbon nanotubes.
  • a partition plate or the like is inserted between the upper region A and the lower region B in the porous structure 14, and the dispersion liquid phase A present in the region A and the dispersion liquid present in the region B Recover phase B respectively.
  • the cutting blade 50 may be used as part of the partition plate.
  • the method of twisting the porous structure 14 with the separation tank 11 is mentioned, for example, as shown in FIG.
  • the separation tank 11 one composed of a film composed of a resin such as an acrylic resin is used. While the direct current voltage is applied to the first electrode 12 and the second electrode 13, the porous structure 14 is twisted together with the separation tank 11 at the center in the height direction of the separation tank 11 and the porous structure 14.
  • the porous structure 14 is divided into a region A containing many metallic single-walled carbon nanotubes and a region B containing many semiconducting single-walled carbon nanotubes. Then, the dispersion liquid phase A present in the upper region A of the divided porous structure 14 and the dispersion liquid phase B present in the lower region B of the porous structure 14 are recovered.
  • the recovered dispersion is again accommodated in the separation tank 11, and the metal single-walled carbon nanotube and the semiconducting single-walled carbon nanotube contained in the single-walled carbon nanotube dispersion are separated by electrophoresis in the same manner as described above.
  • metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes of high purity can be obtained.
  • the separation efficiency of the recovered dispersion was determined by the change in Raman spectrum of the Radial Breathing Mode (RBM) region, the change of the Raman spectrum shape of the Breit-Wigner-Fano (BWF) region, and the UV-visible near-red color. It can evaluate by methods, such as an external absorption spectrophotometric analysis (change of the peak shape of an absorption spectrum).
  • the separation efficiency of the dispersion can also be evaluated by evaluating the electrical characteristics of the single-walled carbon nanotube. For example, the separation efficiency of the dispersion can be evaluated by fabricating a field effect transistor and measuring the transistor characteristics.
  • metal single-walled carbon nanotubes are efficiently recovered from the region A of the porous structure 14
  • the semiconductor single-walled carbon nanotubes can be efficiently recovered from the region B of the porous structure 14.
  • FIG. 6 is a schematic view showing the nanocarbon separation device of the present embodiment.
  • the nanocarbon separation apparatus 100 includes a separation tank (electrophoresis tank) 11, a first electrode 12 provided on the upper side in the separation tank 11, and a second electrode provided on the lower side in the separation tank 11. And a porous structure 101 provided between the first electrode 12 and the second electrode 13 in the separation tank 11 so as to extend along the height direction of the separation tank 11; And.
  • the porous structure 101 is an aggregate of a plurality of particles 102.
  • the porous structure 101 is an assembly of a plurality of particles 102 filled between the first electrode 12 and the second electrode 13 in the separation tank 11.
  • the particles 102 are not particularly limited as long as they form a gap between the particles when the particles 102 are packed in the separation tank 11 in the closest packing manner.
  • Examples of the particles 102 include spherical particles, diamond-shaped particles, tetrapod (registered trademark) particles, and the like.
  • the gaps formed between the particles 102 correspond to a plurality of regions formed by the inside of the separation tank 11 being partitioned by the porous structure 101.
  • the material of the particle 102 is not particularly limited as long as it is stable to the nanocarbon dispersion liquid 30 and is an insulating material.
  • Examples of the material of the particles 102 include glass, quartz, acrylic resin, and the like.
  • the filling amount of the particles 102 to the separation tank 11 is not particularly limited, and is appropriately set according to the amount (volume) of the nanocarbon dispersion liquid 30 contained in the separation tank 11.
  • the particles 102 may have any structure as long as the nanocarbon micelles can pass through and voids can be continuously connected to form a potential gradient between the upper and lower electrodes.
  • the average particle diameter of the particles 102 is preferably 1 ⁇ m or more and 1 cm or less, and more preferably 10 ⁇ m or more and 1 mm or less. If the average particle diameter of the particles 102 is 1 ⁇ m or more, a gap to be described later occurs between the particles 102 filled in the separation tank 11, so separation of the dispersion 30 of nanocarbon using the nanocarbon separation device 10
  • the porous structure 14 does not disturb the movement of the metallic nanocarbon and the semiconducting nanocarbon contained in the dispersion liquid 30 of nanocarbon. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
  • the porosity of the porous structure 101 is determined in the same manner as the porosity of the porous structure 14 described above.
  • the size of the pores of the porous structure 101 is preferably 40 nm or more, more preferably 100 n ⁇ m or more, and more than 200 nm. Is more desirable.
  • the inner diameter of the pores is preferably 1 cm or less, more preferably 1 mm or less.
  • the porous structure 101 is included in the nanocarbon dispersion 30 in the separation of the nanocarbon dispersion 30 using the nanocarbon separation device 100 It does not prevent the movement of metallic nanocarbon and semiconducting nanocarbon. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
  • the shape of the pores of the porous structure 101 is indeterminate, for example, spherical or spheroidal. Therefore, the inner diameter of the pores of the porous structure 101 means the diameter of the sphere when the pores are spherical, the major diameter of the spheroid when the pores are spheroid, and the pores In the case of shapes other than spherical and spheroidal, it is the length of the longest part of the shape.
  • the pore size of the porous structure 101 is determined in the same manner as the pore size of the porous structure 14 described above.
  • the porous structure 101 that is, the particles 102 constituting the porous structure 101, is transparent in order to facilitate confirmation of the separation state of the metallic nanocarbon and the semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30. It is preferable that it is milky white translucent (white that the back is visible), milky white (non-transparent, non-transparent white).
  • the nanocarbon separation apparatus 100 of the present embodiment may include an injection port (not shown) for injecting the dispersion liquid 30 of nanocarbon into the separation tank 11 as in the first embodiment.
  • the nanocarbon separation apparatus 100 of this embodiment is not limited to this.
  • the first electrode 12 may be an anode
  • the second electrode 13 may be a cathode.
  • a porous structure 101 composed of a plurality of particles 102 filled in the separation tank 11 is provided between the first electrode 12 and the second electrode 13.
  • dispersion of nanocarbon in separation tank 11 The occurrence of horizontal flow in the liquid 30 can be suppressed. Therefore, metallic nanocarbon and semiconducting nanocarbon can be separated rapidly. Therefore, metal nanocarbon and semiconductor nanocarbon with high purity can be obtained.
  • the method of separating nanocarbon includes the step of injecting the dispersion 30 of nanocarbon into the separation tank 11 (injection step), and the first electrode 12 and the second electrode. 13 has a step (separation step) of applying a DC voltage to separate the metal nanocarbon and the semiconductor nanocarbon contained in the nanocarbon dispersion liquid 30.
  • injection step the nanocarbon dispersion liquid 30 is injected into the separation tank 11 so that the first electrode 12 and the second electrode 13 are in contact with the nanocarbon dispersion liquid 30.
  • the first electrode 12 and the second electrode 13 are immersed in the nanocarbon dispersion liquid 30.
  • the nanocarbon separation method of the present embodiment is different from the first embodiment nanocarbon separation method described above in that a plurality of particles 102 are filled in the separation tank 11 to form a porous structure 101, It is a point which divides the inside of separation tank 11 into a plurality of fields.
  • a horizontal flow is generated in the single-walled carbon nanotube dispersion liquid. Can be suppressed.
  • the region A including the dispersion liquid phase A is rapidly formed in the region on the first electrode 12 side in the porous structure 101, and the porous structure A region B containing the dispersion liquid phase B can be formed in the region on the second electrode 13 side in 14, and the single-walled carbon nanotube dispersion liquid can be phase-separated into the dispersion liquid phase A and the dispersion liquid phase B.
  • the single-walled carbon nanotube dispersion liquid in the separation tank 11 it is possible to suppress the occurrence of the flow in the horizontal direction.
  • metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes can be separated rapidly.
  • metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes with high purity can be obtained.
  • the case of separating a mixture of single-walled carbon nanotubes into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes has been exemplified.
  • the separation method is not limited to this.
  • the method of separating nanocarbons of the present embodiment for example, after separating into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes in the separation tank 11, only single-walled carbon nanotubes having desired properties are recovered.
  • the method may be performed as a method of purifying single-walled carbon nanotubes.
  • the porous structure 101 is replaced with the metal type single-walled carbon nanotube. It is divided into a region A containing a large amount and a region B containing a large amount of semiconducting single-walled carbon nanotubes, metal single-walled carbon nanotubes are recovered from the region A, and semiconducting single-walled carbon nanotubes are collected from the region B.
  • the recovery method is not particularly limited, and any method may be used as long as the dispersion liquid phase A and the dispersion liquid phase B do not diffuse and mix.
  • the nanocarbon recovery method of the present embodiment as the recovery method, for example, the same method as in the first embodiment is used.
  • the recovered dispersion is again accommodated in the separation tank 11, and the single-walled carbon nanotube dispersion and the semiconductor single-walled carbon nanotube contained in the single-walled carbon nanotube dispersion by electrophoresis.
  • the operation of separating single-walled carbon nanotubes may be repeated.
  • the separation efficiency of the recovered dispersion can be evaluated in the same manner as in the first embodiment.
  • metal single-walled carbon nanotubes are efficiently recovered from the region A of the porous structure 101
  • the semiconductor single-walled carbon nanotubes can be efficiently recovered from the region B of the porous structure 101.
  • FIG. 7 is a schematic view showing a nanocarbon separation device of the present embodiment. 7, the same reference numerals as in the nanocarbon separation device of the first embodiment shown in FIG. 1 and the nanocarbon separation device of the second embodiment shown in FIG. Duplicate descriptions will be omitted.
  • the nanocarbon separation apparatus 200 of the present embodiment includes a separation tank (electrophoresis tank) 11, a first electrode 202 provided in the upper part in the separation tank 11, and a second electrode provided in the lower part in the separation tank 11. And a porous structure 101 provided between the first electrode 202 and the second electrode 203 in the separation tank 11 so as to extend along the height direction of the separation tank 11; And.
  • the first electrode 202 is composed of a particle 102 constituting the top layer of the porous structure 101 and an electrode particle 110 having a metal film 103 formed on the surface of the particle 102.
  • the second electrode 203 is composed of an electrode particle 110 having a particle 102 constituting the lowermost layer of the porous structure 101 and a metal film 103 formed on the surface of the particle 102.
  • the first electrode 202 and the second electrode 203 are arranged such that the plurality of electrode particles 110 are in contact with each other.
  • Conductor wires 204 and 205 are connected to a part of electrode particles 110 constituting the first electrode 202 and the second electrode 203.
  • the conducting wires 204 and 205 are drawn out of the separation tank 11.
  • the metal film 103 is made of a metal such as platinum. Although it does not specifically limit as method to form the metal film 103, For example, vapor deposition, electrolytic plating, electroless plating etc. are mentioned.
  • the nanocarbon separation apparatus 200 of the present embodiment is provided at the lower end of the separation tank 11 with an injection / recovery port 16 communicating with the inner bottom surface 11 a of the separation tank 11.
  • the injection / recovery port 16 is used to inject the nanocarbon dispersion liquid 30 into the separation tank 11 and to collect the nanocarbon dispersion liquid 30 from the separation tank 11.
  • the injection / recovery port 16 may be provided with a closed structure such as a rotary cock 17 having a fit.
  • a part of the separation tank 11 which constitutes the inner bottom surface 11a and communicates with the injection / recovery port 16 has a tapered shape in which the width (diameter) gradually decreases toward the injection / recovery port 16 side.
  • the change in liquid level at the time of injection / recovery It is not necessary to move the injection / recovery port in accordance with the above, and the injection / recovery operation can be performed without disturbing the liquid phase interface inside the separation tank 11.
  • the capacity of the separation tank 11 is increased, it is very rational without the need to prepare a long injection / recovery nozzle.
  • the nanocarbon separation apparatus 200 of this embodiment is not limited to this.
  • the first electrode 202 may be an anode
  • the second electrode 203 may be a cathode.
  • the first electrode 202 includes the particles 102 constituting the uppermost layer of the porous structure 101, and the electrode particles having the metal film 103 formed on the surface of the particles 102.
  • the second electrode 203 is composed of a particle 102 constituting the lowermost layer of the porous structure 101 and an electrode particle 110 having a metal film 103 formed on the surface of the particle 102.
  • the second electrode 203 is made of the electrode particles 110, and the porous structure 101 is made of a plurality of particles 102 filled in the separation tank 11.
  • the particle 102 and the electrode particle 110 can move freely by setting the particle 102 and the electrode particle when the injection / recovery nozzle is inserted into the separation tank 11 through the injection / recovery port 16. 110 does not disturb the inlet / recovery nozzle. Therefore, the injection and recovery of the nanocarbon dispersion liquid 30 into the separation tank 11 can be smoothly performed via the injection / recovery port 16. Further, according to the nanocarbon separation apparatus 200 of the present embodiment, the porous structure 101 formed of the plurality of particles 102 filled in the separation tank 11 is formed between the first electrode 202 and the second electrode 203.
  • step of separating metallic nanocarbon and semiconducting nanocarbon contained in dispersion liquid of nanocarbon for example, implementing the separation method of nanocarbon described later, by providing the nanocarbon in separation tank 11 It is possible to suppress the occurrence of horizontal flow in the dispersion liquid 30 of Therefore, metallic nanocarbon and semiconducting nanocarbon can be separated rapidly. Therefore, metal nanocarbon and semiconductor nanocarbon with high purity can be obtained.
  • the method of separating nanocarbon includes the step of injecting the dispersion 30 of nanocarbon into the separation tank 11 (injection step), and the first electrode 202 and the second electrode. It has a process (separation process) which applies a direct current voltage to 203 and separates metallic nanocarbon and semiconducting nanocarbon contained in the dispersion liquid 30 of nanocarbon.
  • injection step the nanocarbon dispersion liquid 30 is injected into the separation tank 11 so that the first electrode 202 and the second electrode 203 are in contact with the nanocarbon dispersion liquid 30.
  • the first electrode 202 and the second electrode 203 are immersed in the nanocarbon dispersion liquid 30.
  • a plurality of particles 102 are filled in the separation tank 11 to form the porous structure 101, and the inside of the separation tank 11 is partitioned into a plurality of regions.
  • the region A including the dispersion liquid phase A is rapidly formed in the region on the first electrode 202 side of the porous structure 101, and the porous structure A single-walled carbon nanotube dispersion liquid can be phase-separated into the dispersion liquid phase A and the dispersion liquid phase B by forming the area B containing the dispersion liquid phase B in the area on the second electrode 203 side in.
  • the porous structure 101 formed of an aggregate of the plurality of particles 102 between the first electrode 202 and the second electrode 203.
  • the case of separating a mixture of single-walled carbon nanotubes into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes has been exemplified.
  • the separation method is not limited to this.
  • metal single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes are separated in the separation tank 11, and then only single-walled carbon nanotubes having desired properties are recovered. You may carry out as a purification method of a single-walled carbon nanotube.
  • the porous structure 101 is replaced by metal single-walled carbon nanotubes. It is divided into a region A containing a large amount and a region B containing a large amount of semiconducting single-walled carbon nanotubes, metal single-walled carbon nanotubes are recovered from the region A, and semiconducting single-walled carbon nanotubes are collected from the region B.
  • the recovery method is not particularly limited, and any method may be used as long as the dispersion liquid phase A and the dispersion liquid phase B do not diffuse and mix.
  • the nanocarbon recovery method of the present embodiment as the recovery method, for example, the same method as in the first embodiment is used.
  • the recovered dispersion is again accommodated in the separation tank 11, and the single-walled carbon nanotube dispersion and the semiconductor single-walled carbon nanotube contained in the single-walled carbon nanotube dispersion by electrophoresis.
  • the operation of separating single-walled carbon nanotubes may be repeated.
  • the separation efficiency of the recovered dispersion can be evaluated in the same manner as in the first embodiment.
  • metal nanocarbon is efficiently recovered from the region A of the porous structure 101.
  • the semiconductor nanocarbon can be efficiently recovered from the region B of the porous structure 101.
  • a separation method of nanocarbon using the nanocarbon separation device 10 will be described with reference to FIG.
  • a single-walled carbon nanotube dispersion in which a mixture of single-walled carbon nanotubes is dispersed in an aqueous solution in which water and a nonionic surfactant are dissolved, and an aqueous solution containing 2 wt% of a nonionic surfactant are prepared.
  • water is gently injected into the separation tank 11 from an injection / recovery port (not shown) provided at the lower end of the separation tank 11 using a perister pump or the like.
  • the single-walled carbon nanotube dispersion liquid is injected into the separation tank 11.
  • an aqueous solution having a nonionic surfactant content of 2 wt% is injected into the separation tank 11.
  • the region in contact with the first electrode 12 is water
  • the region in contact with the second electrode 13 is a 2 wt% aqueous solution
  • the middle region is a single-walled carbon nanotube dispersion.
  • the first electrode 12 is in contact with only water
  • the second electrode 13 is in contact with only a 2 wt% aqueous solution.
  • the first electrode 12 and the second electrode 13 are not in contact with the single-walled carbon nanotube dispersion liquid.
  • the mixture of single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion liquid is separated into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
  • the method for separating nanocarbons of the present embodiment can also be applied to the first to third embodiments described above.
  • the nanocarbon separation apparatus of the present invention can reduce the time required for separation in the separation of a mixture of nanocarbons.

Abstract

This nanocarbon separation device (10) comprises: a separation tank (11) that stores a dispersion that includes nanocarbon; a first electrode (12) that is provided at an upper part of the inside of the separation tank (11); a second electrode (13) that is provided at a lower part of the inside of the separation tank (11); and a porous structure (14) that is provided inside the separation tank (11) between the first electrode (12) and the second electrode (13).

Description

ナノカーボン分離装置、ナノカーボンの分離方法、ナノカーボンの回収方法Nano carbon separation device, separation method of nano carbon, recovery method of nano carbon
本発明は、ナノカーボン分離装置、ナノカーボンの分離方法およびナノカーボンの回収方法に関する。 The present invention relates to a nanocarbon separation device, a nanocarbon separation method, and a nanocarbon recovery method.
単層カーボンナノチューブは、高い電子移動度を持ち、その機械的特性、電気的特性、化学的特性等から様々な分野への適用が期待されている。単層カーボンナノチューブは、半導体性と金属性の異なる性質を持つ材料が２：１の割合で含まれる混合物として合成されるため、工業的に応用するためには、性質毎に高純度かつ速やかに分離を行う必要がある。 Single-walled carbon nanotubes have high electron mobility, and their application to various fields is expected from their mechanical properties, electrical properties, chemical properties, and the like. Single-walled carbon nanotubes are synthesized as a mixture containing materials with different properties of semiconductivity and metallicity in a ratio of 2: 1. Therefore, for industrial application, high purity and rapidity per property are achieved. Need to do separation.
　単層カーボンナノチューブの混合物を分離する方法としては、例えば、異なる複数の電荷を持つナノカーボンミセル群に分散した、ナノカーボン材料の分散溶液と、ナノカーボン材料と異なる比重を持つ保持溶液とを、電気泳動槽内に所定の方向に積層して導入配置する工程と、積層して導入配置した分散溶液と保持溶液に、直列方向に直流電圧を印加することにより、該ナノカーボンミセル群を２以上のナノカーボンミセル群に分離する工程と、を含むナノカーボン材料分離方法が知られている（例えば、特許文献１参照）。また、単層カーボンナノチューブを非イオン性界面活性剤溶液中へ分散した単層カーボンナノチューブ含有ミセル分散溶液に対して縦型に設置された分離槽内で直流電圧を印加し、各ミセルが全体として正電荷を有する金属性単層カーボンナノチューブの濃縮されている単層カーボンナノチューブ含有ミセル分散液層と、各ミセルが全体としては極めて弱い電荷しか有しない半導体性単層カーボンナノチューブ含有ミセル分散液の層との、少なくとも２層に分離する工程を有する単層カーボンナノチューブ分離方法であって、直流電圧が、分離槽の上部に設置された陰極と、下部設置された陽極とにより印加され、電界の向きが重力方向と平行で上方に向いている単層カーボンナノチューブ分離方法が知られている（例えば、特許文献２参照）。 As a method of separating a mixture of single-walled carbon nanotubes, for example, a dispersion solution of a nanocarbon material dispersed in nanocarbon micelles having different charges, and a holding solution having a different specific gravity from the nanocarbon material, The step of stacking and introducing in a predetermined direction in the electrophoresis tank, and applying a DC voltage in series to the dispersed solution and the holding solution which are stacked and introduced, two or more of the nanocarbon micelle groups And a step of separating into a group of nano carbon micelles of (1), (2). In addition, a DC voltage is applied to the single-walled carbon nanotube-containing micelle dispersion solution in which single-walled carbon nanotubes are dispersed in a non-ionic surfactant solution in a separation tank vertically disposed, and each micelle as a whole A concentrated single-walled carbon nanotube-containing micelle dispersion liquid layer in which metallic single-walled carbon nanotubes having positive charges are concentrated, and a layer of semiconductive single-walled carbon nanotube-containing micelle dispersion liquid in which each micelle has a very weak charge as a whole. A method of separating single-walled carbon nanotubes, comprising the step of separating into at least two layers, wherein a direct current voltage is applied by the cathode disposed at the top of the separation vessel and the anode disposed at the bottom, and the direction of the electric field There is known a method of separating single-walled carbon nanotubes, in which the direction is parallel to the direction of gravity and points upward (see, for example, Patent Document 2) .
特許第５５４１２８３号公報Patent No. 5541283 gazette 特許第５７１７２３３号公報Patent No. 5717233 gazette
しかしながら、特許文献１および２に記載の分離方法では、一度に多量の単層カーボンナノチューブの混合物を分離するために、分離槽の直径を拡大すると、直径の拡大に伴って、分離槽内において、単層カーボンナノチューブを含む分散液の対流等による擾乱が生じて、分離に時間を要するという課題があった。 However, in the separation methods described in Patent Documents 1 and 2, when the diameter of the separation tank is expanded in order to separate a mixture of a large amount of single-walled carbon nanotubes at one time, the diameter increases as the diameter increases. There is a problem that disturbance due to convection or the like of the dispersion containing single-walled carbon nanotubes occurs, and it takes time for separation.
本発明は、ナノカーボンの混合物の分離において、分離に要する時間を短縮する、ナノカーボン分離装置、ナノカーボンの分離方法およびナノカーボンの回収方法を提供することを目的とする。 An object of the present invention is to provide a nanocarbon separation device, a nanocarbon separation method, and a nanocarbon recovery method, in which the time required for separation is reduced in the separation of a mixture of nanocarbons.
本発明のナノカーボン分離装置は、ナノカーボンを含む分散液を収容する分離槽と、前記分離槽内の上部に設けられた第１の電極と、前記分離槽内の下部に設けられた第２の電極と、前記分離槽内にて前記第１の電極と前記第２の電極の間に設けられた多孔質構造物と、を備える。 A nanocarbon separation apparatus according to the present invention comprises a separation vessel for containing a dispersion containing nanocarbon, a first electrode provided in the upper part in the separation vessel, and a second part provided in the lower part in the separation vessel. And a porous structure provided between the first electrode and the second electrode in the separation tank.
　本発明のナノカーボンの分離方法は、本発明のナノカーボン分離装置を用いたナノカーボンの分離方法であって、前記分離槽にナノカーボンを含む分散液を注入する工程と、前記第１の電極と前記第２の電極に直流電圧を印加し、前記分散液に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程と、を有する。 The method for separating nanocarbons according to the present invention is a method for separating nanocarbons using the apparatus for separating nanocarbons according to the present invention, comprising the steps of: injecting a dispersion containing nanocarbon into the separation tank; and the first electrode And applying a DC voltage to the second electrode to separate the metal nanocarbon and the semiconductor nanocarbon contained in the dispersion.
　本発明のナノカーボンの回収方法は、本発明のナノカーボン分離装置を用いたナノカーボンの回収方法であって、前記ナノカーボン分離装置による分離操作が終了した後、前記多孔質構造物を、金属型ナノカーボンを多く含む領域Ａと半導体型ナノカーボンを多く含む領域Ｂとに分割し、前記領域Ａから前記金属型ナノカーボンを回収し、前記領域Ｂから前記半導体型ナノカーボンを回収する。 The method for recovering nano carbon of the present invention is a method for recovering nano carbon using the nano carbon separation device of the present invention, wherein the porous structure is treated with a metal after the separation operation by the nano carbon separation device is completed. The region is divided into a region A containing a large amount of nanocarbon and a region B containing a large amount of semiconductor nanocarbon, the metal nanocarbon is recovered from the region A, and the semiconductor nanocarbon is collected from the region B.
本発明によれば、ナノカーボンの混合物の分離において、分離に要する時間を短縮することができる。 According to the present invention, in the separation of a mixture of nanocarbons, the time required for the separation can be shortened.
第１の実施形態のナノカーボン分離装置を示す模式図である。It is a schematic diagram which shows the nanocarbon separation apparatus of 1st Embodiment. 第１の実施形態のナノカーボン分離装置を示す模式図である。It is a schematic diagram which shows the nanocarbon separation apparatus of 1st Embodiment. 本発明のナノカーボンの分離方法を示すフローチャートである。It is a flowchart which shows the separation method of the nanocarbon of this invention. 第１の実施形態のナノカーボン分離装置におけるナノカーボンの回収方法を示す模式図である。It is a schematic diagram which shows the collection | recovery method of nanocarbon in the nanocarbon separation apparatus of 1st Embodiment. 第１の実施形態のナノカーボン分離装置におけるナノカーボンの回収方法を示す模式図である。It is a schematic diagram which shows the collection | recovery method of nanocarbon in the nanocarbon separation apparatus of 1st Embodiment. 第２の実施形態のナノカーボン分離装置を示す模式図である。It is a schematic diagram which shows the nanocarbon separation apparatus of 2nd Embodiment. 第３の実施形態のナノカーボン分離装置を示す模式図である。It is a schematic diagram which shows the nanocarbon separation apparatus of 3rd Embodiment. 第４の実施形態のナノカーボン分離装置を示す斜視図である。It is a perspective view which shows the nanocarbon separation apparatus of 4th Embodiment.
本発明のナノカーボン分離装置、ナノカーボンの分離方法およびナノカーボンの回収方法の実施の形態について説明する。
なお、本実施の形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。 An embodiment of a nanocarbon separation device, a nanocarbon separation method, and a nanocarbon recovery method of the present invention will be described.
The present embodiment is specifically described in order to better understand the spirit of the invention, and does not limit the present invention unless otherwise specified.
［第１の実施形態］多孔質構造物：スポンジ
（ナノカーボン分離装置）
図１は、本実施形態のナノカーボン分離装置を示す模式図である。
本実施形態のナノカーボン分離装置１０は、分離槽（電気泳動槽）１１と、分離槽１１内の上部に設けられた第１の電極１２と、分離槽１１内の下部に設けられた第２の電極１３と、分離槽１１内にて第１の電極１２と第２の電極１３の間に、分離槽１１の高さ方向に沿って延在するように設けられた多孔質構造物１４と、を備える。
本実施形態のナノカーボン分離装置１０では、多孔質構造物１４が、内部に細かな孔が無数に空いた多孔質の柔らかい物体であるスポンジからなる。 First Embodiment Porous Structure: Sponge (Nano Carbon Separation Device)
FIG. 1 is a schematic view showing a nanocarbon separation device of the present embodiment.
The nanocarbon separation apparatus 10 according to the present embodiment includes a separation tank (electrophoresis tank) 11, a first electrode 12 provided in the upper part in the separation tank 11, and a second electrode provided in the lower part in the separation tank 11. And a porous structure 14 provided between the first electrode 12 and the second electrode 13 in the separation tank 11 so as to extend along the height direction of the separation tank 11; And.
In the nanocarbon separation device 10 of the present embodiment, the porous structure 14 is made of a sponge which is a porous soft body having numerous fine holes therein.
第１の電極１２は、分離槽１１内にて、その高さ方向の上方（分離槽１１内にて、その高さの半分より上の領域、分離槽１１の内底面１１ａとは反対側の領域）に配置されている。
第２の電極１３は、分離槽１１内にて、その高さ方向の下方（分離槽１１内にて、その高さの半分より下の領域、分離槽１１の内底面１１ａ側の領域）に配置されている。
本実施形態のナノカーボン分離装置１０において、第１の電極１２が陰極、第２の電極１３が陽極である。この場合、第１の電極１２と第２の電極１３に直流電圧を印加すると、電界の向きが分離槽１１の下方から上方へ向かう。 The first electrode 12 is located in the upper side in the height direction in the separation tank 11 (in the area above the half of the height in the separation tank 11, on the opposite side to the inner bottom surface 11 a of the separation tank 11) Area) is arranged.
The second electrode 13 is located in the lower part in the height direction in the separation tank 11 (in the area below the half of the height in the separation tank 11, the area on the inner bottom surface 11a side of the separation tank 11) It is arranged.
In the nanocarbon separation device 10 of the present embodiment, the first electrode 12 is a cathode, and the second electrode 13 is an anode. In this case, when a DC voltage is applied to the first electrode 12 and the second electrode 13, the direction of the electric field is directed upward from below the separation tank 11.
　分離槽１１は、ナノカーボンを含む分散液（以下、「ナノカーボンの分散液」という。）３０を収容可能な空間を有する。分離槽１１は、電気泳動により、収容したナノカーボンの分散液３０に分散した、ナノカーボンの分離を行うためのものである。分離槽１１は、ナノカーボンの分散液３０を収容できるものであれば、その形状や大きさは特に限定されない。 The separation tank 11 has a space capable of accommodating a dispersion liquid containing nanocarbon (hereinafter, referred to as “nanocarbon dispersion liquid”) 30. The separation tank 11 is for separating nanocarbon dispersed in the contained nanocarbon dispersion liquid 30 by electrophoresis. The shape and size of the separation tank 11 are not particularly limited as long as the separation tank 11 can accommodate the nanocarbon dispersion liquid 30.
　分離槽１１は、中空管を有する容器である。分離槽１１の下端は閉じられており、容器の底になっている。 The separation tank 11 is a container having a hollow tube. The lower end of the separation tank 11 is closed and is the bottom of the container.
　分離槽１１の材質は、ナノカーボンの分散液３０に対して安定であり、かつ絶縁性の材質であれば特に限定されない。分離槽１１の材質としては、例えば、ガラス、石英、アクリル樹脂等が挙げられる。 The material of the separation tank 11 is not particularly limited as long as it is stable to the nanocarbon dispersion liquid 30 and is an insulating material. As a material of the separation tank 11, glass, quartz, an acrylic resin etc. are mentioned, for example.
　第１の電極１２および第２の電極１３としては、電気泳動に用いることができ、ナノカーボンの分散液３０に対して安定なものであれば特に限定されない。第１の電極１２および第２の電極１３としては、例えば、白金電極等が挙げられる。 The first electrode 12 and the second electrode 13 can be used for electrophoresis, and are not particularly limited as long as they are stable with respect to the nanocarbon dispersion liquid 30. Examples of the first electrode 12 and the second electrode 13 include a platinum electrode and the like.
　第１の電極１２および第２の電極１３の構造は、特に限定されず、分離槽１１内において、多孔質構造物１４によって区画される領域の形状や大きさに応じて適宜選択される。第１の電極１２の構造は、多孔質構造物１４の上部に配置され、かつ分離槽１１内において、多孔質構造物１４の上端の全域に拡がるように配置されるものであれば特に限定されない。第２の電極１３の構造としては、多孔質構造物１４の下部に配置され、かつ分離槽１１内において、多孔質構造物１４の下端の全域に拡がるように配置されるものであれば特に限定されない。第１の電極１２および第２の電極１３の構造としては、例えば、分離槽１１の平面視において、円環状、円板状、棒状等が挙げられる。また、第１の電極１２および第２の電極１３の構造としては、多数の微細孔が均質に設けられた多孔板状が挙げられる。 The structure of the first electrode 12 and the second electrode 13 is not particularly limited, and may be appropriately selected according to the shape and size of the area partitioned by the porous structure 14 in the separation tank 11. The structure of the first electrode 12 is not particularly limited as long as it is disposed on the top of the porous structure 14 and disposed so as to extend over the entire top end of the porous structure 14 in the separation tank 11. . The structure of the second electrode 13 is particularly limited as long as it is disposed in the lower part of the porous structure 14 and disposed so as to extend over the entire lower end of the porous structure 14 in the separation tank 11. I will not. Examples of the structure of the first electrode 12 and the second electrode 13 include, in a plan view of the separation tank 11, an annular shape, a disk shape, a rod shape, and the like. Moreover, as a structure of the 1st electrode 12 and the 2nd electrode 13, the porous-plate shape in which many micropores were provided uniformly is mentioned.
　多孔質構造物１４をなすスポンジとしては、特に限定されない。スポンジの材質は、ナノカーボンの分散液３０に対して安定であり、かつ絶縁性の材質であれば特に限定されない。スポンジは、内部に細かな孔が連続的につながり、無数に空いた多孔質体である。スポンジとしては、天然の海綿からなるもの、合成樹脂からなる人造のスポンジ等が挙げられる。また、スポンジの材質としては、次のような溶液を保持できる多孔質材料を用いることができる。多孔質材料としては、例えば、ウレタン；発泡ポリエチレン、ポリエチレン、エチレンプロピレンゴム、クロロプレンゴム、天然ゴム、メラミン樹脂等を利用した合成スポンジ類；モクヨカイメンに代表される海面生物により産出される天然スポンジ；軽石等が挙げられる。さらに、一例を挙げるならば、空孔率９８．５％であるウレタンフォーム製吸水用スポンジ（そのような例；トラスコ中山 ＴＲＵＳＣＯ 吸水スポンジ)を用いることができる。よって、スポンジからなる多孔質構造物１４によって、分離槽１１内が多数の領域に区画される。 The sponge that forms the porous structure 14 is not particularly limited. The material of the sponge is not particularly limited as long as it is stable to the nanocarbon dispersion liquid 30 and is an insulating material. The sponge is a porous body in which fine pores are continuously connected inside and innumerably opened. Examples of the sponge include those made of natural sponge, and artificial sponges made of synthetic resin. Moreover, as a material of a sponge, the porous material which can hold | maintain the following solutions can be used. As the porous material, for example, urethane; synthetic sponges using foamed polyethylene, polyethylene, ethylene propylene rubber, chloroprene rubber, natural rubber, melamine resin etc .; natural sponge produced by sea surface organisms represented by Mok yokaimen; pumice stone Etc. Furthermore, if an example is given, the urethane foam water absorption sponge (The such example; TRUSCO NAKAYAMA TRUSCO water absorption sponge) which is 98.5% of the porosity can be used. Therefore, the inside of the separation tank 11 is divided into a large number of regions by the porous structure 14 made of a sponge.
　多孔質構造物１４の大きさ（高さ、外径、体積等）は、特に限定されず、多孔質構造物１４に保持させるナノカーボンの分散液３０の量に応じて、適宜調整される。 The size (height, outer diameter, volume, etc.) of the porous structure 14 is not particularly limited, and is appropriately adjusted according to the amount of the nanocarbon dispersion liquid 30 to be held by the porous structure 14.
　多孔質構造物１４における多孔率（多孔度）は、ナノカーボンミセルが通過でき、かつ、連続的に孔がつながり、上下の電極間に対して電位勾配が形成されるならば、いかなる多孔率をとっても良い。合成スポンジにおいては、多孔質構造物１４における多孔率（多孔度）は、８０％以上９９．９％以下であることが好ましく、９０％以上９９％以下であることがより好ましい。なお、合成スポンジにおいては、多孔質構造物１４における多孔率が８０％以上であれば、多孔質構造物１４の全域において、細孔が連通し、ナノカーボン分離装置１０を用いたナノカーボンの分散液３０の分離において、多孔質構造物１４がナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンの移動を妨げることがない。これにより、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを効率的に分離することができる。 The porosity (porosity) in the porous structure 14 is any porosity as long as the nanocarbon micelles can pass through and pores are continuously connected to form a potential gradient between the upper and lower electrodes. It is very good. In the synthetic sponge, the porosity (porosity) of the porous structure 14 is preferably 80% to 99.9%, and more preferably 90% to 99%. In the synthetic sponge, when the porosity in the porous structure 14 is 80% or more, the pores communicate with each other throughout the porous structure 14, and the dispersion of nanocarbons using the nanocarbon separation device 10 In the separation of the liquid 30, the porous structure 14 does not prevent the movement of the metallic nanocarbon and the semiconductive nanocarbon contained in the nanocarbon dispersion liquid 30. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
　多孔質構造物１４の多孔率は、多孔質構造物１４の総体積に対して、多孔質構造物１４の細孔が占める割合である。多孔質構造物１４の多孔率は、下記の式（１）で表わされる。
ａ１／Ａ１×１００・・・（１）
すなわち、多孔質構造物１４の多孔率は、多孔質構造物１４の細孔の全体積ａ１と、細孔を含む多孔質構造物１４の全体積Ａ１との比の百分率で表わされる。 The porosity of the porous structure 14 is a ratio of the pores of the porous structure 14 to the total volume of the porous structure 14. The porosity of the porous structure 14 is represented by the following formula (1).
a1 / A1 × 100 (1)
That is, the porosity of the porous structure 14 is expressed as a percentage of the ratio of the total area al of the pores of the porous structure 14 to the total area Al of the porous structure 14 including the pores.
　多孔質構造物１４の多孔率を求める方法としては、例えば、細孔を含む多孔質構造物１４の見かけの比重ｄ１と、含む多孔質構造物１４の真の比重Ｄ１とを求め、それらの比重から、多孔質構造物１４の多孔率を算出する方法が挙げられる。この方法では、下記の式（２）に基づいて、多孔質構造物１４の多孔率を算出する。
　（Ｄ１－ｄ１）／Ｄ１×１００・・・（２） As a method of determining the porosity of the porous structure 14, for example, the apparent specific gravity d1 of the porous structure 14 including pores and the true specific gravity D1 of the porous structure 14 including are determined, and those specific gravity From the above, a method of calculating the porosity of the porous structure 14 can be mentioned. In this method, the porosity of the porous structure 14 is calculated based on the following equation (2).
(D1-d1) / D1 × 100 (2)
　多孔質構造物１４の細孔の大きさ、すなわち、細孔の内径は、４０ｎｍ以上であることが好ましく、１００ｎｍ以上であることがより好ましく、２００ｎｍよりも大きいことがさらに好ましい。また、細孔の内径は、１ｃｍ以下であることが好ましく、より好ましくは１ｍｍ以下である。
多孔質構造物１４の細孔の内径が４０ｎｍ以上であれば、ナノカーボン分離装置１０を用いたナノカーボンの分散液３０の分離において、多孔質構造物１４がナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンの移動を妨げることがない。これにより、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを効率的に分離することができる。 The size of the pores of the porous structure 14, that is, the inner diameter of the pores is preferably 40 nm or more, more preferably 100 nm or more, and still more preferably more than 200 nm. The inner diameter of the pores is preferably 1 cm or less, more preferably 1 mm or less.
When the inner diameter of the pores of the porous structure 14 is 40 nm or more, the porous structure 14 is included in the nanocarbon dispersion 30 in the separation of the nanocarbon dispersion 30 using the nanocarbon separation device 10 It does not prevent the movement of metallic nanocarbon and semiconducting nanocarbon. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
　なお、多孔質構造物１４の細孔の形状は、不定形であり、例えば、球体状、回転楕円体状等をなしている。そのため、多孔質構造物１４の細孔の内径とは、細孔が球体状をなす場合には球体の直径、細孔が回転楕円体状をなす場合には回転楕円体の長径、細孔が球体状および回転楕円体状以外の形状をなす場合にはその形状の最も長い部分の長さのこととする。 In addition, the shape of the pores of the porous structure 14 is indeterminate, and for example, it has a spherical shape, a spheroid shape, or the like. Therefore, the inner diameter of the pores of the porous structure 14 means the diameter of the sphere when the pores are spherical, the major diameter of the spheroid when the pores are spheroid, and the pores In the case of shapes other than spherical and spheroidal, it is the length of the longest part of the shape.
　多孔質構造物１４の細孔の大きさを求める方法としては、例えば、多孔質構造物１４を光学顕微鏡や走査型電子顕微鏡で観察し、その顕微鏡像から細孔の大きさを実測する方法等が挙げられる。 As a method of determining the size of the pores of the porous structure 14, for example, a method of observing the porous structure 14 with an optical microscope or a scanning electron microscope and measuring the size of the pores from the microscopic image, etc. Can be mentioned.
　多孔質構造物１４は、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンの分離状態を確認し易くするために、透明、乳白色半透明（裏が透けて見える白色）、乳白色（裏が透けない、透明ではない白色）であることが好ましい。金属型ナノカーボンと半導体型ナノカーボンの分離が進行すると、金属型ナノカーボンの含有量が多いナノカーボンの分散液３０は黒色となり、半導体型ナノカーボンの含有量が多いナノカーボンの分散液３０は青色となる。そこで、多孔質構造物１４の色を背景として、金属型ナノカーボンと半導体型ナノカーボンの分離状態を、目視にて確認することが好ましい。 The porous structure 14 is transparent, milky white and translucent (white in which the back is seen through), in order to make it easy to confirm the separation state of the metallic nanocarbon and the semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30. It is preferable that it is milky white (the back is opaque and it is white which is not transparent). When the separation of the metallic nanocarbon and the semiconducting nanocarbon proceeds, the dispersion 30 of the nanocarbon having a large content of the metallic nanocarbon turns black, and the dispersion 30 of the nanocarbon having a large content of the semiconducting nanocarbon It becomes blue. Therefore, it is preferable to visually confirm the separation state of the metallic nanocarbon and the semiconducting nanocarbon on the background of the color of the porous structure 14.
　多孔質構造物１４は、分離槽１１内にて第１の電極１２と第２の電極１３の間の領域にて、その領域の高さ方向のほぼ全域にわたって延在することが好ましい。また、多孔質構造物１４の外形は、分離槽１１内にて第１の電極１２と第２の電極１３の間の領域の形状に相似の形状であることが好ましい。 The porous structure 14 preferably extends in the separation tank 11 in the region between the first electrode 12 and the second electrode 13 over substantially the entire height direction of the region. The outer shape of the porous structure 14 is preferably similar to the shape of the region between the first electrode 12 and the second electrode 13 in the separation tank 11.
本実施形態のナノカーボン分離装置１０は、分離槽１１内にナノカーボンの分散液３０を注入する注入口（図示略）を備えていてもよい。注入口は、分離槽１１にて、その高さ方向の上方（分離槽１１にて、その高さの半分より上の領域、分離槽１１の内底面１１ａとは反対側の領域）に設けられていてもよい。分離槽１１の上端を開口部１１ｂとした場合、その開口部１１ｂが、分離槽１１内にナノカーボンの分散液３０を注入する注入口であってもよい。 The nanocarbon separation apparatus 10 of the present embodiment may include an injection port (not shown) for injecting the dispersion liquid 30 of nanocarbon into the separation tank 11. The inlet is provided at the upper side in the height direction in the separation tank 11 (in the area above the half of the height in the separation tank 11, the area on the opposite side to the inner bottom surface 11a of the separation tank 11) It may be When the upper end of the separation tank 11 is an opening 11 b, the opening 11 b may be an injection port for injecting the dispersion 30 of nanocarbon into the separation tank 11.
本実施形態のナノカーボン分離装置１０では、第１の電極１２が陰極、第２の電極１３が陽極である場合を例示したが、本実施形態のナノカーボン分離装置１０はこれに限定されない。本実施形態のナノカーボン分離装置１０にあっては、第１の電極１２が陽極、第２の電極１３が陰極であってもよい。 Although the case where the 1st electrode 12 is a cathode and the 2nd electrode 13 is an anode was illustrated in nanocarbon separation device 10 of this embodiment, nanocarbon separation device 10 of this embodiment is not limited to this. In the nanocarbon separation apparatus 10 of the present embodiment, the first electrode 12 may be an anode, and the second electrode 13 may be a cathode.
　本実施形態のナノカーボン分離装置１０によれば、第１の電極１２と第２の電極１３の間に、分離槽１１の高さ方向に沿って延在するように設けられた多孔質構造物１４を設けることにより、例えば、後述するナノカーボンの分離方法を実施する、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程において、分離槽１１内にて、ナノカーボンの分散液３０に水平方向の流れが生じるのを抑制することができる。したがって、金属型ナノカーボンと半導体型ナノカーボンを迅速に分離することができる。よって、純度が高い金属型ナノカーボンと半導体型ナノカーボンを得ることができる。 According to the nanocarbon separation apparatus 10 of the present embodiment, a porous structure provided so as to extend along the height direction of the separation tank 11 between the first electrode 12 and the second electrode 13 In the step of separating metal-type nanocarbon and semiconductor-type nanocarbon contained in dispersion liquid 30 of nanocarbon, for example, implementing the separation method of nanocarbon described later by providing 14. The occurrence of horizontal flow in the nanocarbon dispersion liquid 30 can be suppressed. Therefore, metallic nanocarbon and semiconducting nanocarbon can be separated rapidly. Therefore, metal nanocarbon and semiconductor nanocarbon with high purity can be obtained.
（ナノカーボンの分離方法）
　図１～図３を用いて、ナノカーボン分離装置１０を用いた、ナノカーボンの分離方法を説明するとともに、ナノカーボン分離装置１０の作用を説明する。
　図３は、本実施形態のナノカーボンの分離方法を示すフローチャートである。 (Separation method of nano carbon)
The method of separating nanocarbons using the nanocarbon separating apparatus 10 will be described using FIGS. 1 to 3, and the operation of the nanocarbon separating apparatus 10 will be described.
FIG. 3 is a flowchart showing the method for separating nanocarbons of the present embodiment.
　本実施形態のナノカーボンの分離方法は、分離槽１１にナノカーボンの分散液３０を注入する工程（以下、「注入工程」という。）と、第１の電極１２と第２の電極１３に直流電圧を印加し、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程（以下、「分離工程」という。）と、を有する。 In the method of separating nanocarbon of the present embodiment, a step of injecting the dispersion 30 of nanocarbon into the separation tank 11 (hereinafter referred to as “injection step”), and direct current to the first electrode 12 and the second electrode 13. And applying a voltage to separate the metallic nanocarbon and the semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 (hereinafter, referred to as “separation step”).
本実施形態のナノカーボンの分離方法において、ナノカーボンとは、単層カーボンナノチューブ、二層カーボンナノチューブ、多層カーボンナノチューブ、カーボンナノホーン、カーボンナノツイス卜、グラフェン、フラーレン等の主に炭素から構成される炭素材料を意味する。本実施形態のナノカーボンの分離方法では、ナノカーボンとして単層カーボンナノチューブが分散した分散液から、半導体型単層カーボンナノチューブと、金属型単層カーボンナノチューブと、を分離する場合について詳述する。 In the method of separating nanocarbons according to the present embodiment, the nanocarbons are mainly composed of carbon such as single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nano-swipe, graphene, fullerene, etc. It means carbon material. In the method of separating nanocarbons of the present embodiment, the case of separating a semiconducting single-walled carbon nanotube and a metallic single-walled carbon nanotube from a dispersion liquid in which single-walled carbon nanotubes are dispersed as nanocarbon will be described in detail.
単層カーボンナノチューブは、チューブの直径、巻き方によって金属型と半導体型という２つの異なる性質に分かれることが知られている。従来の製造方法を用いて単層カーボンナノチューブを合成すると、金属的な性質を有する金属型単層カーボンナノチューブと半導体的な性質を有する半導体型単層カーボンナノチューブが統計的に１：２の割合で含まれる単層カーボンナノチューブの混合物が得られる。 It is known that single-walled carbon nanotubes are divided into two different properties of metallic type and semiconductive type depending on the diameter and winding method of the tube. When single-walled carbon nanotubes are synthesized using a conventional manufacturing method, metallic single-walled carbon nanotubes having metallic properties and semiconducting single-walled carbon nanotubes having semiconducting properties are statistically in a ratio of 1: 2 A mixture of single-walled carbon nanotubes is obtained.
　単層カーボンナノチューブの混合物は、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブとを含むものであれば特に制限されない。また、本実施形態における単層カーボンナノチューブは、単層カーボンナノチューブ単体であってもよいし、一部の炭素が任意の官能基で置換された単層カーボンナノチューブや、任意の官能基で修飾された単層カーボンナノチューブであってもよい。 The mixture of single-walled carbon nanotubes is not particularly limited as long as it contains metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes. In addition, the single-walled carbon nanotube in the present embodiment may be a single-walled carbon nanotube alone, or may be modified with a single-walled carbon nanotube in which a part of carbon is substituted with an arbitrary functional group, or an arbitrary functional group. It may be a single-walled carbon nanotube.
まず、単層カーボンナノチューブの混合物が、界面活性剤とともに分散媒に分散した単層カーボンナノチューブ分散液を調製する。 First, a single-walled carbon nanotube dispersion is prepared in which a mixture of single-walled carbon nanotubes is dispersed in a dispersion medium together with a surfactant.
　分散媒としては、単層カーボンナノチューブの混合物を分散させることができるものであれば特に限定されない。分散媒としては、例えば、水、重水、有機溶媒、イオン液体等が挙げられる。これらの分散媒の中でも、単層カーボンナノチューブが変質しないことから、水または重水が好適に用いられる。 The dispersion medium is not particularly limited as long as the mixture of single-walled carbon nanotubes can be dispersed. Examples of the dispersion medium include water, heavy water, an organic solvent, an ionic liquid and the like. Among these dispersion media, water or heavy water is preferably used because single-walled carbon nanotubes do not deteriorate.
　界面活性剤としては、非イオン性界面活性剤、陽イオン性界面活性剤、陰イオン性界面活性剤等が用いられる。単層カーボンナノチューブにナトリウムイオン等のイオン性の不純物が混入することを防ぐためには、非イオン性界面活性剤を用いることが好ましい。 As surfactant, nonionic surfactant, cationic surfactant, anionic surfactant etc. are used. In order to prevent ionic impurities such as sodium ions from mixing into the single-walled carbon nanotube, it is preferable to use a nonionic surfactant.
　非イオン性界面活性剤としては、イオン化しない親水性部位とアルキル鎖等の疎水性部位とを有する非イオン性界面活性剤が用いられる。このような非イオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル系に代表されるポリエチレングリコール構造を有する非イオン性界面活性剤が挙げられる。
このような非イオン性界面活性剤としては、下記式（１）で表わされるポリオキシエチレンアルキルエーテルが好適に用いられる。
ＣｎＨ２ｎ（ＯＣＨ２ＣＨ２）ｍＯＨ　（１）
（但し、ｎ＝１２～１８、ｍ＝２０～１００である。） As the nonionic surfactant, a nonionic surfactant having a non-ionizing hydrophilic site and a hydrophobic site such as an alkyl chain is used. Examples of such nonionic surfactants include nonionic surfactants having a polyethylene glycol structure represented by polyoxyethylene alkyl ether.
As such a nonionic surfactant, polyoxyethylene alkyl ether represented by the following formula (1) is suitably used.
C n H 2 n (OCH 2 CH 2 ) m OH (1)
(However, n = 12 to 18 and m = 20 to 100.)
　上記式（１）で表わされるポリオキシエチレンアルキルエーテルとしては、例えば、ポリオキシエチレン（２３）ラウリルエーテル（商品名：Ｂｒｉｊ Ｌ２３、シグマアルドリッチ社製）、ポリオキシエチレン（２０）セチルエーテル（商品名：Ｂｒｉｊ Ｃ２０、シグマアルドリッチ社製）、ポリオキシエチレン（２０）ステアリルエーテル（商品名：Ｂｒｉｊ Ｓ２０、シグマアルドリッチ社製）、ポリオキシエチレン（２０）オレイルエーテル（商品名：Ｂｒｉｊ Ｏ２０、シグマアルドリッチ社製）、ポリオキシエチレン（１００）ステアリルエーテル（商品名：Ｂｒｉｊ Ｓ１００、シグマアルドリッチ社製）等が挙げられる。 Examples of the polyoxyethylene alkyl ether represented by the above formula (1) include polyoxyethylene (23) lauryl ether (trade name: Brij L23, manufactured by Sigma Aldrich), polyoxyethylene (20) cetyl ether (trade name) : Brij C20, manufactured by Sigma Aldrich), polyoxyethylene (20) stearyl ether (trade name: Brij S20, manufactured by Sigma Aldrich), polyoxyethylene (20) oleyl ether (trade name: Brij O20, manufactured by Sigma Aldrich) And polyoxyethylene (100) stearyl ether (trade name: Brij S100, manufactured by Sigma Aldrich Co.) and the like.
非イオン性界面活性剤としては、ポリオキシエチレンソルビタンモノステアラート（分子式：Ｃ６４Ｈ１２６Ｏ２６、商品名：Ｔｗｅｅｎ ６０、シグマアルドリッチ社製）、ポリオキシエチレンソルビタントリオレアート（分子式：Ｃ２４Ｈ４４Ｏ６、商品名：Ｔｗｅｅｎ ８５、シグマアルドリッチ社製）、オクチルフェノールエトキシレート（分子式：Ｃ１４Ｈ２２Ｏ（Ｃ２Ｈ４Ｏ）ｎ、ｎ＝１～１０、商品名：Ｔｒｉｔｏｎ Ｘ－１００、シグマアルドリッチ社製）、ポリオキシエチレン（４０）イソオクチルフェニルエーテル（分子式：Ｃ８Ｈ１７Ｃ６Ｈ４０（ＣＨ２ＣＨ２０）４０Ｈ、商品名：Ｔｒｉｔｏｎ Ｘ－４０５、シグマアルドリッチ社製）、ポロキサマー（分子式：Ｃ５Ｈ１０Ｏ２、商品名：Ｐｌｕｒｏｎｉｃ、シグマアルドリッチ社製）、ポリビニルピロリドン（分子式：（Ｃ６Ｈ９ＮＯ）ｎ、ｎ＝５～１００、シグマアルドリッチ社製）等を用いることもできる。 As a nonionic surfactant, polyoxyethylene sorbitan monostearate (molecular formula: C 64 H 126 O 26 , trade name: Tween 60, manufactured by Sigma Aldrich), polyoxyethylene sorbitan trioleate (molecular formula: C 24 H 44 O 6 , trade name: Tween 85, manufactured by Sigma Aldrich, octylphenol ethoxylate (molecular formula: C 14 H 22 O (C 2 H 4 O) n , n = 1 to 10, trade name: Triton X-100, Sigma-Aldrich, polyoxyethylene (40) isooctylphenyl ether (molecular formula: C 8 H 17 C 6 H 40 (CH 2 CH 20 ) 40 H, trade name: Triton X-405, manufactured by Sigma-Aldrich) Poloxamer (molecular formula: C 5 H 10 O 2 , trade name: Pluronic, manufactured by Sigma Aldrich, polyvinyl pyrrolidone (molecular formula: (C 6 H 9 NO) n , n = 5 to 100, manufactured by Sigma Aldrich), or the like can also be used.
単層カーボンナノチューブ分散液における非イオン性界面活性剤の含有量は、０．１ｗｔ％以上５ｗｔ％以下であることが好ましく、０．５ｗｔ％以上２ｗｔ％以下であることがより好ましい。
　非イオン性界面活性剤の含有量が５ｗｔ％以下であれば、単層カーボンナノチューブ分散液の粘度が高くなり過ぎることがなく、電気泳動によって容易に、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離することができる。 The content of the nonionic surfactant in the single-walled carbon nanotube dispersion is preferably 0.1 wt% or more and 5 wt% or less, and more preferably 0.5 wt% or more and 2 wt% or less.
If the content of the nonionic surfactant is 5 wt% or less, the viscosity of the single-walled carbon nanotube dispersion does not become too high, and the metal type contained in the single-walled carbon nanotube dispersion easily by electrophoresis. Single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes can be separated.
　単層カーボンナノチューブ分散液における単層カーボンナノチューブの含有量は、１μｇ／ｍＬ以上１００μｇ／ｍＬ以下であることが好ましく、５μｇ／ｍＬ以上４０μｇ／ｍＬ以下であることがより好ましい。
単層カーボンナノチューブの含有量が上記の範囲であれば、電気泳動によって容易に、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離することができる。 The content of single-walled carbon nanotubes in the single-walled carbon nanotube dispersion liquid is preferably 1 μg / mL or more and 100 μg / mL or less, and more preferably 5 μg / mL or more and 40 μg / mL or less.
If the content of single-walled carbon nanotubes is in the above range, metal single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion can be easily separated by electrophoresis.
　単層カーボンナノチューブ分散液を調製する方法としては、特に限定されず、公知の方法が用いられる。例えば、単層カーボンナノチューブ混合物と界面活性剤を含む分散媒の混合液を超音波処理して、分散媒に、単層カーボンナノチューブ混合物を分散させる方法が挙げられる。この超音波処理により、凝集していた金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブが充分に分離し、単層カーボンナノチューブ分散液は、分散媒に金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブが均一に分散したものとなる。したがって、後述する電気泳動法により、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離し易くなる。なお、超音波処理により分散しなかった金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブは、超遠心分離により分離、除去することが好ましい。 The method of preparing the single-walled carbon nanotube dispersion is not particularly limited, and known methods may be used. For example, there is a method in which a mixture of a single-walled carbon nanotube mixture and a dispersion medium containing a surfactant is subjected to ultrasonication to disperse the single-walled carbon nanotube mixture in the dispersion medium. By this ultrasonic treatment, the aggregated metal single-walled carbon nanotubes and the semiconductor single-walled carbon nanotubes are sufficiently separated, and the single-walled carbon nanotube dispersion liquid contains metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes as a dispersion medium. The multi-walled carbon nanotubes become uniformly dispersed. Therefore, metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes can be easily separated by the electrophoresis method described later. Preferably, metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes not dispersed by ultrasonication are separated and removed by ultracentrifugation.
　次いで、注入工程にて、上述のように調製した単層カーボンナノチューブ分散液を、分離槽１１に注入する。
　これにより、単層カーボンナノチューブ分散液が、分離槽１１内の多孔質構造物１４に浸潤する。
　また、分離槽１１に単層カーボンナノチューブ分散液を注入することにより、単層カーボンナノチューブ分散液に第１の電極１２と第２の電極１３が接する。本実施形態では、単層カーボンナノチューブ分散液に第１の電極２０２と第２の電極２０３を浸漬した。なお、多孔質構造物１４に第１の電極１２と第２の電極１３が接している必要はない。 Next, in the injection step, the single-walled carbon nanotube dispersion prepared as described above is injected into the separation tank 11.
Thereby, the single-walled carbon nanotube dispersion liquid infiltrates the porous structure 14 in the separation tank 11.
In addition, by injecting the single-walled carbon nanotube dispersion liquid into the separation tank 11, the first electrode 12 and the second electrode 13 are in contact with the single-walled carbon nanotube dispersion liquid. In the present embodiment, the first electrode 202 and the second electrode 203 are immersed in the single-walled carbon nanotube dispersion liquid. The first electrode 12 and the second electrode 13 do not have to be in contact with the porous structure 14.
　次いで、分離工程にて、電気泳動法により、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離する。 Next, in the separation step, metallic single-walled carbon nanotubes and semiconductive single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion liquid are separated by electrophoresis.
第１の電極１２と第２の電極１３に、所定時間（例えば、１時間～２４時間）、直流電圧を印加することにより、分離槽１１内にて、電界を形成する。具体的には、電界の向きが分離槽１１の下方から上方へ向かうように電界を形成する。この電界と、単層カーボンナノチューブの電荷とにより生じる電気泳動力により、単層カーボンナノチューブ分散液に含まれる単層カーボンナノチューブの混合物が、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブとに分離される。 An electric field is formed in the separation tank 11 by applying a DC voltage to the first electrode 12 and the second electrode 13 for a predetermined time (for example, 1 hour to 24 hours). Specifically, the electric field is formed such that the direction of the electric field is from the bottom to the top of the separation tank 11. A mixture of single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion is a metallic single-walled carbon nanotube and a semiconducting single-walled carbon nanotube by the electric field generated by the electric field and the charge of the single-walled carbon nanotube. It is separated.
非イオン性界面活性剤を含む単層カーボンナノチューブ分散液中では、金属型単層カーボンナノチューブが正電荷を有し、半導体型単層カーボンナノチューブが極めて弱い負電荷を有する。 In the single-walled carbon nanotube dispersion liquid containing the nonionic surfactant, the metallic single-walled carbon nanotube has a positive charge, and the semiconducting single-walled carbon nanotube has an extremely weak negative charge.
　したがって、第１の電極１２と第２の電極１３に直流電圧を印加すると、単層カーボンナノチューブ分散液に含まれる単層カーボンナノチューブの混合物のうち、金属型単層カーボンナノチューブが第１の電極１２（陰極）側に移動し、半導体型単層カーボンナノチューブが第２の電極１３（陽極）側に移動する。その結果として、単層カーボンナノチューブ分散液は、相対的に金属型単層カーボンナノチューブの含有量が多い分散液相（以下、「分散液相Ａ」という。）と、相対的に半導体型単層カーボンナノチューブの含有量が多い分散液相（以下、「分散液相Ｂ」という。）と、分散液相Ａと分散液相Ｂの間に形成され、相対的に金属型単層カーボンナノチューブおよび半導体型単層カーボンナノチューブの含有量が少ない分散液相（以下、「分散液相Ｃ」という。）との３相に相分離する。 Therefore, when a DC voltage is applied to the first electrode 12 and the second electrode 13, the metallic single-walled carbon nanotube is the first electrode 12 among the mixture of single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion. It moves to the (cathode) side, and the semiconductor single-walled carbon nanotube moves to the second electrode 13 (anode) side. As a result, the single-walled carbon nanotube dispersion has a relatively semiconductive-type single-walled dispersion liquid phase (hereinafter referred to as “dispersed liquid phase A”) having a relatively high content of metallic single-walled carbon nanotubes. A dispersed liquid phase (hereinafter referred to as “dispersed liquid phase B”) having a large content of carbon nanotubes, and formed between the dispersed liquid phase A and the dispersed liquid phase B, the metal single-walled carbon nanotubes and the semiconductor are relatively formed. Phase separation into three phases with a dispersion liquid phase (hereinafter referred to as “dispersion liquid phase C”) having a low content of single-walled carbon nanotubes.
　言い換えれば、多孔質構造物１４における第１の電極１２側の領域には、金属型単層カーボンナノチューブを多く含む領域Ａ、すなわち、分散液相Ａを含む領域が形成される。また、多孔質構造物１４における第２の電極１３側の領域には、半導体型単層カーボンナノチューブを多く含む領域Ｂ、すなわち、分散液相Ｂを含む領域が形成される。 In other words, in the region on the first electrode 12 side of the porous structure 14, the region A containing a large amount of metallic single-walled carbon nanotubes, that is, a region containing the dispersed liquid phase A is formed. Further, in the region on the second electrode 13 side in the porous structure 14, a region B containing a large amount of semiconductor single-walled carbon nanotubes, that is, a region containing the dispersed liquid phase B is formed.
　第１の電極１２と第２の電極１３に印加する直流電圧は、特に限定されず、第１の電極１２と第２の電極１３との間の距離や単層カーボンナノチューブ分散液における単層カーボンナノチューブの混合物の含有量等に応じて適宜調整される。 The direct current voltage applied to the first electrode 12 and the second electrode 13 is not particularly limited, and the distance between the first electrode 12 and the second electrode 13 or single-walled carbon in the single-walled carbon nanotube dispersion liquid It is suitably adjusted according to the content of the mixture of nanotubes and the like.
　単層カーボンナノチューブ分散液の分散媒として、水または重水を用いた場合、第１の電極１２と第２の電極１３に印加する直流電圧を、０Ｖより大きく、１０００Ｖ以下の間の任意の値とする。 When water or heavy water is used as a dispersion medium for the single-walled carbon nanotube dispersion, the DC voltage applied to the first electrode 12 and the second electrode 13 is an arbitrary value between 0 V and 1000 V or less. Do.
　例えば、第１の電極１２と第２の電極１３の距離（電極間距離）が３０ｃｍである場合、第１の電極１２と第２の電極１３に印加する直流電圧は、１５Ｖ以上４５０Ｖ以下であることが好ましく、３０Ｖ以上３００Ｖ以下であることがより好ましい。
　第１の電極１２と第２の電極１３に印加する直流電圧が１５Ｖ以上であれば、分離槽１１内にて、単層カーボンナノチューブ分散液のｐＨ勾配を形成して、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離することができる。一方、第１の電極１２と第２の電極１３に印加する直流電圧が４５０Ｖ以下であれば、水または重水の電気分解による影響を抑えられる。 For example, when the distance between the first electrode 12 and the second electrode 13 (inter-electrode distance) is 30 cm, the DC voltage applied to the first electrode 12 and the second electrode 13 is 15 V or more and 450 V or less Is preferable, and more preferably 30 V or more and 300 V or less.
If the DC voltage applied to the first electrode 12 and the second electrode 13 is 15 V or more, a pH gradient of the single-walled carbon nanotube dispersion liquid is formed in the separation tank 11, and the single-walled carbon nanotube dispersion liquid Can separate the metallic single-walled carbon nanotubes and the semiconducting single-walled carbon nanotubes from each other. On the other hand, if the DC voltage applied to the first electrode 12 and the second electrode 13 is 450 V or less, the influence of the electrolysis of water or heavy water can be suppressed.
　また、第１の電極１２と第２の電極１３に直流電圧を印加したとき、第１の電極１２と第２の電極１３の間の電界は、０．５Ｖ／ｃｍ以上１５Ｖ／ｃｍ以下であることが好ましく、１Ｖ／ｃｍ以上１０Ｖ／ｃｍ以下であることがより好ましい。
　第１の電極１２と第２の電極１３の間の電界が０．５Ｖ／ｃｍ以上であれば、分離槽１１内にて、単層カーボンナノチューブ分散液のｐＨ勾配を形成して、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離することができる。一方、第１の電極１２と第２の電極１３の間の電界が１５Ｖ／ｃｍ以下であれば、水または重水の電気分解による影響を抑えられる。 In addition, when a DC voltage is applied to the first electrode 12 and the second electrode 13, the electric field between the first electrode 12 and the second electrode 13 is 0.5 V / cm or more and 15 V / cm or less Is preferable, and more preferably 1 V / cm or more and 10 V / cm or less.
If the electric field between the first electrode 12 and the second electrode 13 is 0.5 V / cm or more, a pH gradient of the single-walled carbon nanotube dispersion liquid is formed in the separation tank 11 to obtain single-walled carbon The metallic single-walled carbon nanotubes and the semiconducting single-walled carbon nanotubes contained in the nanotube dispersion liquid can be separated. On the other hand, if the electric field between the first electrode 12 and the second electrode 13 is 15 V / cm or less, the influence of the electrolysis of water or heavy water can be suppressed.
　ところで、電気泳動法により、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブの分離を開始すると、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブが、分離槽１１の高さ方向に沿って移動するとともに、分離槽１１の高さ方向と垂直な方向にも移動する。これにより、単層カーボンナノチューブ分散液に、分離槽１１の高さ方向と垂直な方向（水平方向）に流れが生じる。単層カーボンナノチューブ分散液に水平方向の流れが生じると、単層カーボンナノチューブ分散液を分散液相Ａと分散液相Ｂに相分離するための時間が長くなる。特に、分離槽１１の容積が大きくなるに伴って、分離槽１１の内径が拡大した場合、相分離に要する時間が長くなる。そこで、本実施形態では、分離槽１１内に、スポンジから構成される多孔質構造物１４を設けて、分離槽１１内を多数の領域に区画している。これにより、分離工程において、電気泳動法によって、分離槽１１内にて、単層カーボンナノチューブ分散液を相分離する際、単層カーボンナノチューブ分散液に水平方向の流れが生じるのを抑制することができる。その結果、内径が大きな分離槽１１を用いた場合にも、迅速に、多孔質構造物１４における第１の電極１２側の領域に分散液相Ａを含む領域Ａを形成し、多孔質構造物１４における第２の電極１３側の領域に分散液相Ｂを含む領域Ｂを形成して、単層カーボンナノチューブ分散液を分散液相Ａと分散液相Ｂに相分離することができる。 When separation of metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes is started by electrophoresis, metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes are aligned along the height direction of the separation tank 11. And move in a direction perpendicular to the height direction of the separation tank 11. As a result, the single-walled carbon nanotube dispersion liquid flows in the direction (horizontal direction) perpendicular to the height direction of the separation tank 11. When a flow in the horizontal direction occurs in the single-walled carbon nanotube dispersion, the time for phase-separating the single-walled carbon nanotube dispersion into the dispersed liquid phase A and the dispersed liquid phase B becomes long. In particular, when the inner diameter of the separation tank 11 increases as the volume of the separation tank 11 increases, the time required for phase separation becomes longer. So, in this embodiment, the porous structure 14 comprised from sponge is provided in the separation tank 11, and the inside of the separation tank 11 is divided into many area | regions. Thereby, in the separation step, when the single-walled carbon nanotube dispersion liquid is phase-separated in the separation tank 11 by the electrophoresis method, generation of a horizontal flow in the single-walled carbon nanotube dispersion liquid is suppressed it can. As a result, even when the separation tank 11 having a large inner diameter is used, the region A including the dispersion liquid phase A is rapidly formed in the region on the first electrode 12 side in the porous structure 14, and the porous structure A region B containing the dispersion liquid phase B can be formed in the region on the second electrode 13 side in 14, and the single-walled carbon nanotube dispersion liquid can be phase-separated into the dispersion liquid phase A and the dispersion liquid phase B.
　本実施形態のナノカーボン分離装置１０を用いたナノカーボンの分離方法によれば、第１の電極１２と第２の電極１３の間に、スポンジからなる多孔質構造物１４を設けることにより、分離槽１１内にて、単層カーボンナノチューブ分散液に水平方向の流れが生じるのを抑制することができる。この結果、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを迅速に分離することができる。よって、純度が高い金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを得ることができる。 According to the separation method of nanocarbon using the nanocarbon separation device 10 of the present embodiment, separation is performed by providing the porous structure 14 made of a sponge between the first electrode 12 and the second electrode 13. In the tank 11, it can suppress that the flow of a horizontal direction arises in a single-walled carbon nanotube dispersion liquid. As a result, metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes can be separated rapidly. Thus, metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes with high purity can be obtained.
　なお、本実施形態のナノカーボンの分離方法では、単層カーボンナノチューブの混合物を、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離する場合を例示したが、本実施形態のナノカーボンの分離方法はこれに限定されない。本実施形態のナノカーボンの分離方法は、例えば、分離槽１１内にて、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離した後、目的の性質を有する単層カーボンナノチューブのみを回収する、単層カーボンナノチューブの精製方法として行ってもよい。 In the method of separating nanocarbons of the present embodiment, the case of separating a mixture of single-walled carbon nanotubes into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes has been exemplified. The separation method is not limited to this. In the method of separating nanocarbons of the present embodiment, for example, after separating into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes in the separation tank 11, only single-walled carbon nanotubes having desired properties are recovered. The method may be performed as a method of purifying single-walled carbon nanotubes.
（ナノカーボンの回収方法）
　本実施形態のナノカーボンの回収方法は、本実施形態のナノカーボン分離装置１０を用いたナノカーボンの分離方法による分離操作が終了した後、多孔質構造物１４を、金属型単層カーボンナノチューブを多く含む領域Ａと半導体型単層カーボンナノチューブを多く含む領域Ｂとに分割し、領域Ａから金属型単層カーボンナノチューブを回収し、領域Ｂから半導体型単層カーボンナノチューブを回収する。 (Recovery method of nano carbon)
In the method for recovering nanocarbon of the present embodiment, after the separation operation by the method for separating nanocarbon using the nanocarbon separation device 10 of the present embodiment is completed, the porous structure 14 is replaced by metal single-walled carbon nanotubes. It is divided into a region A containing a large amount and a region B containing a large amount of semiconducting single-walled carbon nanotubes, metal single-walled carbon nanotubes are recovered from the region A, and semiconducting single-walled carbon nanotubes are collected from the region B.
　回収方法は、特に限定されず、分散液相Ａと分散液相Ｂが拡散混合しない方法であればいかなる方法であってもよい。
　本実施形態のナノカーボンの回収方法では、回収方法としては、例えば、次のような２つの方法が用いられる。 The recovery method is not particularly limited, and any method may be used as long as the dispersion liquid phase A and the dispersion liquid phase B do not diffuse and mix.
In the nanocarbon recovery method of the present embodiment, for example, the following two methods are used as the recovery method.
　回収方法としては、例えば、図４に示すように、切断刃５０を用いる方法が挙げられる。
　この回収方法では、第１の電極１２と第２の電極１３に直流電圧を印加したまま、切断刃５０により、多孔質構造物１４を、その高さ方向において上下に切断して、多孔質構造物１４を、金属型単層カーボンナノチューブを多く含む領域Ａと半導体型単層カーボンナノチューブを多く含む領域Ｂに分割する。また、分割と同時に、多孔質構造物１４における上側の領域Ａと下側の領域Ｂの間に仕切り板等を挿入し、領域Ａに存在する分散液相Ａと、領域Ｂに存在する分散液相Ｂとをそれぞれ回収する。なお、切断刃５０を仕切り板の一部として用いてもよい。 As a collection | recovery method, as shown in FIG. 4, the method of using the cutting blade 50 is mentioned, for example.
In this recovery method, the porous structure 14 is cut up and down in the height direction by the cutting blade 50 while a direct current voltage is applied to the first electrode 12 and the second electrode 13 so that the porous structure is formed. The object 14 is divided into a region A containing many metallic single-walled carbon nanotubes and a region B containing many semiconducting single-walled carbon nanotubes. Further, simultaneously with the division, a partition plate or the like is inserted between the upper region A and the lower region B in the porous structure 14, and the dispersion liquid phase A present in the region A and the dispersion liquid present in the region B Recover phase B respectively. The cutting blade 50 may be used as part of the partition plate.
　また、回収方法としては、例えば、図５に示すように、分離槽１１とともに多孔質構造物１４を捻る方法が挙げられる。
　この回収方法では、分離槽１１としては、アクリル樹脂等の樹脂から構成されるフィルムからなるものが用いられる。第１の電極１２と第２の電極１３に直流電圧を印加したまま、分離槽１１と多孔質構造物１４の高さ方向の中央部にて、分離槽１１とともに多孔質構造物１４を捻って、多孔質構造物１４を、金属型単層カーボンナノチューブを多く含む領域Ａと半導体型単層カーボンナノチューブを多く含む領域Ｂに分割する。そして、分割した多孔質構造物１４における上側の領域Ａに存在する分散液相Ａと、多孔質構造物１４における下側の領域Ｂに存在する分散液相Ｂとをそれぞれ回収する。 Moreover, as a collection | recovery method, the method of twisting the porous structure 14 with the separation tank 11 is mentioned, for example, as shown in FIG.
In this recovery method, as the separation tank 11, one composed of a film composed of a resin such as an acrylic resin is used. While the direct current voltage is applied to the first electrode 12 and the second electrode 13, the porous structure 14 is twisted together with the separation tank 11 at the center in the height direction of the separation tank 11 and the porous structure 14. The porous structure 14 is divided into a region A containing many metallic single-walled carbon nanotubes and a region B containing many semiconducting single-walled carbon nanotubes. Then, the dispersion liquid phase A present in the upper region A of the divided porous structure 14 and the dispersion liquid phase B present in the lower region B of the porous structure 14 are recovered.
　回収した分散液を、再び、分離槽１１に収容し、上述と同様にして、電気泳動法により、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離する操作を繰り返し実施することにより、純度が高い金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを得ることができる。 The recovered dispersion is again accommodated in the separation tank 11, and the metal single-walled carbon nanotube and the semiconducting single-walled carbon nanotube contained in the single-walled carbon nanotube dispersion are separated by electrophoresis in the same manner as described above. By repeating the above operation, metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes of high purity can be obtained.
　回収した分散液の分離効率は、顕微Ｒａｍａｎ分光分析法（Ｒａｄｉａｌ　Ｂｒｅａｔｈｉｎｇ　Ｍｏｄｅ（ＲＢＭ）領域のＲａｍａｎスペクトルの変化、Ｂｒｅｉｔ－Ｗｉｇｎｅｒ－Ｆａｎｏ（ＢＷＦ）領域のＲａｍａｎスペクトル形状の変化）、および紫外可視近赤外吸光光度分析法（吸収スペクトルのピーク形状の変化）等の手法により評価することができる。また、単層カーボンナノチューブの電気的特性について評価することによっても、分散液の分離効率を評価することができる。例えば、電界効果トランジスタを作製して、そのトランジスタ特性を測定することによって、分散液の分離効率を評価することができる。 The separation efficiency of the recovered dispersion was determined by the change in Raman spectrum of the Radial Breathing Mode (RBM) region, the change of the Raman spectrum shape of the Breit-Wigner-Fano (BWF) region, and the UV-visible near-red color. It can evaluate by methods, such as an external absorption spectrophotometric analysis (change of the peak shape of an absorption spectrum). The separation efficiency of the dispersion can also be evaluated by evaluating the electrical characteristics of the single-walled carbon nanotube. For example, the separation efficiency of the dispersion can be evaluated by fabricating a field effect transistor and measuring the transistor characteristics.
　本実施形態のナノカーボンの回収方法によれば、本実施形態のナノカーボンの分離方法による分離操作が終了した後、多孔質構造物１４の領域Ａから金属型単層カーボンナノチューブを効率的に回収することができ、多孔質構造物１４の領域Ｂから半導体型単層カーボンナノチューブを効率的に回収することができる。 According to the method of recovering nano carbon of the present embodiment, after the separation operation by the method of separating nano carbon of the present embodiment is completed, metal single-walled carbon nanotubes are efficiently recovered from the region A of the porous structure 14 The semiconductor single-walled carbon nanotubes can be efficiently recovered from the region B of the porous structure 14.
［第２の実施形態］複数の粒子の集合体
（ナノカーボン分離装置）
図６は、本実施形態のナノカーボン分離装置を示す模式図である。
なお、図６において、図１に示した第１の実施形態のナノカーボン分離装置と同一の構成には同一の符号を付し、重複する説明を省略する。
本実施形態のナノカーボン分離装置１００は、分離槽（電気泳動槽）１１と、分離槽１１内の上部に設けられた第１の電極１２と、分離槽１１内の下部に設けられた第２の電極１３と、分離槽１１内にて第１の電極１２と第２の電極１３の間に、分離槽１１の高さ方向に沿って延在するように設けられた多孔質構造物１０１と、を備える。
本実施形態のナノカーボン分離装置１００では、多孔質構造物１０１が、複数の粒子１０２の集合体である。 Second Embodiment Aggregate of Multiple Particles (Nanocarbon Separation Device)
FIG. 6 is a schematic view showing the nanocarbon separation device of the present embodiment.
In addition, in FIG. 6, the same code | symbol is attached | subjected to the structure same as the nanocarbon separation apparatus of 1st Embodiment shown in FIG. 1, and the overlapping description is abbreviate | omitted.
The nanocarbon separation apparatus 100 according to this embodiment includes a separation tank (electrophoresis tank) 11, a first electrode 12 provided on the upper side in the separation tank 11, and a second electrode provided on the lower side in the separation tank 11. And a porous structure 101 provided between the first electrode 12 and the second electrode 13 in the separation tank 11 so as to extend along the height direction of the separation tank 11; And.
In the nanocarbon separation device 100 of the present embodiment, the porous structure 101 is an aggregate of a plurality of particles 102.
多孔質構造物１０１は、分離槽１１内にて第１の電極１２と第２の電極１３の間に充填された複数の粒子１０２の集合体である。粒子１０２としては、分離槽１１内に最密に充填した場合に、粒子間に隙間が生じる形状のものであれば特に限定されない。粒子１０２としては、例えば、球状の粒子、撒菱状の粒子、テトラポッド（登録商標）状の粒子等が挙げられる。 The porous structure 101 is an assembly of a plurality of particles 102 filled between the first electrode 12 and the second electrode 13 in the separation tank 11. The particles 102 are not particularly limited as long as they form a gap between the particles when the particles 102 are packed in the separation tank 11 in the closest packing manner. Examples of the particles 102 include spherical particles, diamond-shaped particles, tetrapod (registered trademark) particles, and the like.
このような粒子１０２を、分離槽１１内に充填することにより、粒子１０２同士の間に隙間が生じて、多孔質構造物１０１が形成される。粒子１０２同士の間に生じた隙間が、多孔質構造物１０１によって、分離槽１１内が区画されてできる複数の領域に相当する。 By filling such particles 102 in the separation tank 11, a gap is generated between the particles 102, and the porous structure 101 is formed. The gaps formed between the particles 102 correspond to a plurality of regions formed by the inside of the separation tank 11 being partitioned by the porous structure 101.
粒子１０２の材質は、ナノカーボンの分散液３０に対して安定であり、かつ絶縁性の材質であれば特に限定されない。粒子１０２の材質としては、例えば、ガラス、石英、アクリル樹脂等が挙げられる。 The material of the particle 102 is not particularly limited as long as it is stable to the nanocarbon dispersion liquid 30 and is an insulating material. Examples of the material of the particles 102 include glass, quartz, acrylic resin, and the like.
粒子１０２の分離槽１１に対する充填量は、特に限定されず、分離槽１１内に収容されるナノカーボンの分散液３０の量（体積）に応じて適宜設定される。 The filling amount of the particles 102 to the separation tank 11 is not particularly limited, and is appropriately set according to the amount (volume) of the nanocarbon dispersion liquid 30 contained in the separation tank 11.
粒子１０２は、ナノカーボンミセルが通過でき、かつ、連続的に空隙がつながり、上下の電極間に対して電位勾配が形成されるならば、いかなる構造をとっても良い。例えば、球状のセラミックボールとしたばあい、粒子１０２の平均粒子径は、１μｍ以上１ｃｍ以下であることが好ましく、１０μｍ以上１ｍｍ以下であることがより好ましい。粒子１０２の平均粒子径が１μｍ以上であれば、分離槽１１内に充填した粒子１０２同士の間に、後述する隙間が生じるため、ナノカーボン分離装置１０を用いたナノカーボンの分散液３０の分離において、多孔質構造物１４がナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンの移動を妨げることがない。これにより、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを効率的に分離することができる。 The particles 102 may have any structure as long as the nanocarbon micelles can pass through and voids can be continuously connected to form a potential gradient between the upper and lower electrodes. For example, in the case of spherical ceramic balls, the average particle diameter of the particles 102 is preferably 1 μm or more and 1 cm or less, and more preferably 10 μm or more and 1 mm or less. If the average particle diameter of the particles 102 is 1 μm or more, a gap to be described later occurs between the particles 102 filled in the separation tank 11, so separation of the dispersion 30 of nanocarbon using the nanocarbon separation device 10 In the above, the porous structure 14 does not disturb the movement of the metallic nanocarbon and the semiconducting nanocarbon contained in the dispersion liquid 30 of nanocarbon. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
　多孔質構造物１０１の多孔率は、上述の多孔質構造物１４の多孔率と同様に求められる。 The porosity of the porous structure 101 is determined in the same manner as the porosity of the porous structure 14 described above.
　多孔質構造物１０１の細孔の大きさ、すなわち、粒子１０２同士の間に生じた隙間の大きさは、４０ｎｍ以上であることが好ましく、１００ｎμｍ以上であることがより好ましく、２００ｎｍよりも大きいことがさらに望ましい。また、細孔の内径は、１ｃｍ以下であることが望ましく、より好ましくは１ｍｍ以下であることが好ましい。
多孔質構造物１０１の細孔の内径が４０ｎｍ以上であれば、ナノカーボン分離装置１００を用いたナノカーボンの分散液３０の分離において、多孔質構造物１０１がナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンの移動を妨げることがない。これにより、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを効率的に分離することができる。 The size of the pores of the porous structure 101, that is, the size of the gap generated between the particles 102 is preferably 40 nm or more, more preferably 100 nμm or more, and more than 200 nm. Is more desirable. The inner diameter of the pores is preferably 1 cm or less, more preferably 1 mm or less.
When the inner diameter of the pores of the porous structure 101 is 40 nm or more, the porous structure 101 is included in the nanocarbon dispersion 30 in the separation of the nanocarbon dispersion 30 using the nanocarbon separation device 100 It does not prevent the movement of metallic nanocarbon and semiconducting nanocarbon. Thereby, metallic nanocarbon and semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30 can be efficiently separated.
　なお、多孔質構造物１０１の細孔の形状は、不定形であり、例えば、球体状、回転楕円体状等をなしている。そのため、多孔質構造物１０１の細孔の内径とは、細孔が球体状をなす場合には球体の直径、細孔が回転楕円体状をなす場合には回転楕円体の長径、細孔が球体状および回転楕円体状以外の形状をなす場合にはその形状の最も長い部分の長さのこととする。 The shape of the pores of the porous structure 101 is indeterminate, for example, spherical or spheroidal. Therefore, the inner diameter of the pores of the porous structure 101 means the diameter of the sphere when the pores are spherical, the major diameter of the spheroid when the pores are spheroid, and the pores In the case of shapes other than spherical and spheroidal, it is the length of the longest part of the shape.
　多孔質構造物１０１の細孔の大きさは、上述の多孔質構造物１４の細孔の大きさと同様に求められる。 The pore size of the porous structure 101 is determined in the same manner as the pore size of the porous structure 14 described above.
多孔質構造物１０１、すなわち、多孔質構造物１０１を構成する粒子１０２は、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンの分離状態を確認し易くするために、透明、乳白色半透明（裏が透けて見える白色）、乳白色（裏が透けない、透明ではない白色）であることが好ましい。 The porous structure 101, that is, the particles 102 constituting the porous structure 101, is transparent in order to facilitate confirmation of the separation state of the metallic nanocarbon and the semiconducting nanocarbon contained in the nanocarbon dispersion liquid 30. It is preferable that it is milky white translucent (white that the back is visible), milky white (non-transparent, non-transparent white).
　本実施形態のナノカーボン分離装置１００は、第１の実施形態と同様に、分離槽１１内にナノカーボンの分散液３０を注入する注入口（図示略）を備えていてもよい。 The nanocarbon separation apparatus 100 of the present embodiment may include an injection port (not shown) for injecting the dispersion liquid 30 of nanocarbon into the separation tank 11 as in the first embodiment.
本実施形態のナノカーボン分離装置１００では、第１の電極１２が陰極、第２の電極１３が陽極である場合を例示したが、本実施形態のナノカーボン分離装置１００はこれに限定されない。本実施形態のナノカーボン分離装置１００にあっては、第１の電極１２が陽極、第２の電極１３が陰極であってもよい。 Although the case where the 1st electrode 12 is a cathode and the 2nd electrode 13 is an anode was illustrated by the nanocarbon separation apparatus 100 of this embodiment, the nanocarbon separation apparatus 100 of this embodiment is not limited to this. In the nanocarbon separation apparatus 100 of the present embodiment, the first electrode 12 may be an anode, and the second electrode 13 may be a cathode.
　本実施形態のナノカーボン分離装置１００によれば、第１の電極１２と第２の電極１３の間に、分離槽１１内に充填された複数の粒子１０２からなる多孔質構造物１０１を設けることにより、例えば、後述するナノカーボンの分離方法を実施する、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程において、分離槽１１内にて、ナノカーボンの分散液３０に水平方向の流れが生じるのを抑制することができる。したがって、金属型ナノカーボンと半導体型ナノカーボンを迅速に分離することができる。よって、純度が高い金属型ナノカーボンと半導体型ナノカーボンを得ることができる。 According to the nanocarbon separation apparatus 100 of the present embodiment, a porous structure 101 composed of a plurality of particles 102 filled in the separation tank 11 is provided between the first electrode 12 and the second electrode 13. Thus, for example, in the step of separating metal-type nanocarbon and semiconductor-type nanocarbon contained in dispersion liquid of nanocarbon, which implements the method of separating nanocarbon described later, dispersion of nanocarbon in separation tank 11 The occurrence of horizontal flow in the liquid 30 can be suppressed. Therefore, metallic nanocarbon and semiconducting nanocarbon can be separated rapidly. Therefore, metal nanocarbon and semiconductor nanocarbon with high purity can be obtained.
（ナノカーボンの分離方法）
　図６を用いて、ナノカーボン分離装置１００を用いた、ナノカーボンの分離方法を説明するとともに、ナノカーボン分離装置１００の作用を説明する。 (Separation method of nano carbon)
While demonstrating the separation | isolation method of nanocarbon using the nanocarbon separation apparatus 100 using FIG. 6, the effect | action of the nanocarbon separation apparatus 100 is demonstrated.
　本実施形態のナノカーボンの分離方法は、第１の実施形態と同様に、分離槽１１にナノカーボンの分散液３０を注入する工程（注入工程）と、第１の電極１２と第２の電極１３に直流電圧を印加し、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程（分離工程）と、を有する。
　注入工程にて、分離槽１１にナノカーボンの分散液３０を注入することにより、ナノカーボンの分散液３０に第１の電極１２と第２の電極１３が接する。本実施形態では、ナノカーボンの分散液３０に第１の電極１２と第２の電極１３を浸漬した。 Similar to the first embodiment, the method of separating nanocarbon according to the present embodiment includes the step of injecting the dispersion 30 of nanocarbon into the separation tank 11 (injection step), and the first electrode 12 and the second electrode. 13 has a step (separation step) of applying a DC voltage to separate the metal nanocarbon and the semiconductor nanocarbon contained in the nanocarbon dispersion liquid 30.
In the injection step, the nanocarbon dispersion liquid 30 is injected into the separation tank 11 so that the first electrode 12 and the second electrode 13 are in contact with the nanocarbon dispersion liquid 30. In the present embodiment, the first electrode 12 and the second electrode 13 are immersed in the nanocarbon dispersion liquid 30.
　本実施形態のナノカーボンの分離方法が、上述の第１の実施形態ナノカーボンの分離方法と異なる点は、分離槽１１内に複数の粒子１０２を充填して多孔質構造物１０１を形成し、分離槽１１内を複数の領域に区画する点である。これにより、本実施形態では、分離工程において、電気泳動法によって、分離槽１１内にて、単層カーボンナノチューブ分散液を相分離する際、単層カーボンナノチューブ分散液に水平方向の流れが生じるのを抑制することができる。その結果、内径が大きな分離槽１１を用いた場合にも、迅速に、多孔質構造物１０１における第１の電極１２側の領域に分散液相Ａを含む領域Ａを形成し、多孔質構造物１４における第２の電極１３側の領域に分散液相Ｂを含む領域Ｂを形成して、単層カーボンナノチューブ分散液を分散液相Ａと分散液相Ｂに相分離することができる。 The nanocarbon separation method of the present embodiment is different from the first embodiment nanocarbon separation method described above in that a plurality of particles 102 are filled in the separation tank 11 to form a porous structure 101, It is a point which divides the inside of separation tank 11 into a plurality of fields. Thereby, in the present embodiment, when the single-walled carbon nanotube dispersion liquid is separated in the separation tank 11 by the electrophoresis method in the separation step, a horizontal flow is generated in the single-walled carbon nanotube dispersion liquid. Can be suppressed. As a result, even when the separation tank 11 having a large inner diameter is used, the region A including the dispersion liquid phase A is rapidly formed in the region on the first electrode 12 side in the porous structure 101, and the porous structure A region B containing the dispersion liquid phase B can be formed in the region on the second electrode 13 side in 14, and the single-walled carbon nanotube dispersion liquid can be phase-separated into the dispersion liquid phase A and the dispersion liquid phase B.
　本実施形態のナノカーボン分離装置１００を用いたナノカーボンの分離方法によれば、第１の電極１２と第２の電極１３の間に、複数の粒子１０２の集合体からなる多孔質構造物１０１を設けることにより、分離槽１１内にて、単層カーボンナノチューブ分散液に水平方向の流れが生じるのを抑制することができる。この結果、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを迅速に分離することができる。よって、純度が高い金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを得ることができる。 According to the nanocarbon separation method using the nanocarbon separation device 100 of the present embodiment, a porous structure 101 formed of an aggregate of a plurality of particles 102 between the first electrode 12 and the second electrode 13 By providing the single-walled carbon nanotube dispersion liquid in the separation tank 11, it is possible to suppress the occurrence of the flow in the horizontal direction. As a result, metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes can be separated rapidly. Thus, metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes with high purity can be obtained.
　なお、本実施形態のナノカーボンの分離方法では、単層カーボンナノチューブの混合物を、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離する場合を例示したが、本実施形態のナノカーボンの分離方法はこれに限定されない。本実施形態のナノカーボンの分離方法は、例えば、分離槽１１内にて、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離した後、目的の性質を有する単層カーボンナノチューブのみを回収する、単層カーボンナノチューブの精製方法として行ってもよい。 In the method of separating nanocarbons of the present embodiment, the case of separating a mixture of single-walled carbon nanotubes into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes has been exemplified. The separation method is not limited to this. In the method of separating nanocarbons of the present embodiment, for example, after separating into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes in the separation tank 11, only single-walled carbon nanotubes having desired properties are recovered. The method may be performed as a method of purifying single-walled carbon nanotubes.
（ナノカーボンの回収方法）
　本実施形態のナノカーボンの回収方法は、本実施形態のナノカーボン分離装置１００を用いたナノカーボンの分離方法による分離操作が終了した後、多孔質構造物１０１を、金属型単層カーボンナノチューブを多く含む領域Ａと半導体型単層カーボンナノチューブを多く含む領域Ｂとに分割し、領域Ａから金属型単層カーボンナノチューブを回収し、領域Ｂから半導体型単層カーボンナノチューブを回収する。 (Recovery method of nano carbon)
In the method for recovering nanocarbon of the present embodiment, after the separation operation by the method for separating nanocarbon using the nanocarbon separation device 100 of the present embodiment is completed, the porous structure 101 is replaced with the metal type single-walled carbon nanotube. It is divided into a region A containing a large amount and a region B containing a large amount of semiconducting single-walled carbon nanotubes, metal single-walled carbon nanotubes are recovered from the region A, and semiconducting single-walled carbon nanotubes are collected from the region B.
　回収方法は、特に限定されず、分散液相Ａと分散液相Ｂが拡散混合しない方法であればいかなる方法であってもよい。
　本実施形態のナノカーボンの回収方法では、回収方法としては、例えば、第１の実施形態と同様の方法が用いられる。 The recovery method is not particularly limited, and any method may be used as long as the dispersion liquid phase A and the dispersion liquid phase B do not diffuse and mix.
In the nanocarbon recovery method of the present embodiment, as the recovery method, for example, the same method as in the first embodiment is used.
　また、第１の実施形態と同様にして、回収した分散液を、再び、分離槽１１に収容し、電気泳動法により、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離する操作を繰り返し実施してもよい。 Further, in the same manner as in the first embodiment, the recovered dispersion is again accommodated in the separation tank 11, and the single-walled carbon nanotube dispersion and the semiconductor single-walled carbon nanotube contained in the single-walled carbon nanotube dispersion by electrophoresis. The operation of separating single-walled carbon nanotubes may be repeated.
　回収した分散液の分離効率は、第１の実施形態と同様にして、評価することができる。 The separation efficiency of the recovered dispersion can be evaluated in the same manner as in the first embodiment.
　本実施形態のナノカーボンの回収方法によれば、本実施形態のナノカーボンの分離方法による分離操作が終了した後、多孔質構造物１０１の領域Ａから金属型単層カーボンナノチューブを効率的に回収することができ、多孔質構造物１０１の領域Ｂから半導体型単層カーボンナノチューブを効率的に回収することができる。 According to the method of recovering nano carbon of the present embodiment, after the separation operation by the method of separating nano carbon of the present embodiment is completed, metal single-walled carbon nanotubes are efficiently recovered from the region A of the porous structure 101 The semiconductor single-walled carbon nanotubes can be efficiently recovered from the region B of the porous structure 101.
［第３の実施形態］電極粒子
（ナノカーボン分離装置）
図７は、本実施形態のナノカーボン分離装置を示す模式図である。
なお、図７において、図１に示した第１の実施形態のナノカーボン分離装置および図６に示した第２の実施形態のナノカーボン分離装置と同一の構成には同一の符号を付し、重複する説明を省略する。
本実施形態のナノカーボン分離装置２００は、分離槽（電気泳動槽）１１と、分離槽１１内の上部に設けられた第１の電極２０２と、分離槽１１内の下部に設けられた第２の電極２０３と、分離槽１１内にて第１の電極２０２と第２の電極２０３の間に、分離槽１１の高さ方向に沿って延在するように設けられた多孔質構造物１０１と、を備える。 Third Embodiment Electrode Particles (Nano Carbon Separation Device)
FIG. 7 is a schematic view showing a nanocarbon separation device of the present embodiment.
7, the same reference numerals as in the nanocarbon separation device of the first embodiment shown in FIG. 1 and the nanocarbon separation device of the second embodiment shown in FIG. Duplicate descriptions will be omitted.
The nanocarbon separation apparatus 200 of the present embodiment includes a separation tank (electrophoresis tank) 11, a first electrode 202 provided in the upper part in the separation tank 11, and a second electrode provided in the lower part in the separation tank 11. And a porous structure 101 provided between the first electrode 202 and the second electrode 203 in the separation tank 11 so as to extend along the height direction of the separation tank 11; And.
　第１の電極２０２は、多孔質構造物１０１の最上層を構成する粒子１０２と、粒子１０２の表面に形成された金属膜１０３を有する電極粒子１１０からなる。第２の電極２０３は、多孔質構造物１０１の最下層を構成する粒子１０２と、粒子１０２の表面に形成された金属膜１０３を有する電極粒子１１０からなる。第１の電極２０２および第２の電極２０３は、複数の電極粒子１１０が互いに接するように配置されてなる。第１の電極２０２および第２の電極２０３を構成する電極粒子１１０の一部に、導線２０４，２０５が接続されている。その導線２０４，２０５は、分離槽１１外に引出されている。金属膜１０３は、白金等の金属から構成される。金属膜１０３を形成する方法としては、特に限定されないが、例えば、蒸着、電解めっき、無電解めっき等が挙げられる。 The first electrode 202 is composed of a particle 102 constituting the top layer of the porous structure 101 and an electrode particle 110 having a metal film 103 formed on the surface of the particle 102. The second electrode 203 is composed of an electrode particle 110 having a particle 102 constituting the lowermost layer of the porous structure 101 and a metal film 103 formed on the surface of the particle 102. The first electrode 202 and the second electrode 203 are arranged such that the plurality of electrode particles 110 are in contact with each other. Conductor wires 204 and 205 are connected to a part of electrode particles 110 constituting the first electrode 202 and the second electrode 203. The conducting wires 204 and 205 are drawn out of the separation tank 11. The metal film 103 is made of a metal such as platinum. Although it does not specifically limit as method to form the metal film 103, For example, vapor deposition, electrolytic plating, electroless plating etc. are mentioned.
　本実施形態のナノカーボン分離装置２００は、分離槽１１の下端に、分離槽１１の内底面１１ａに連通する注入／回収口１６を備えている。注入／回収口１６は、分離槽１１にナノカーボンの分散液３０を注入、および、分離槽１１からナノカーボンの分散液３０を回収するために用いられる。また、注入／回収口１６は、すり合わせを有する回転式のコック１７等の密閉構造を備えていてもよい。 The nanocarbon separation apparatus 200 of the present embodiment is provided at the lower end of the separation tank 11 with an injection / recovery port 16 communicating with the inner bottom surface 11 a of the separation tank 11. The injection / recovery port 16 is used to inject the nanocarbon dispersion liquid 30 into the separation tank 11 and to collect the nanocarbon dispersion liquid 30 from the separation tank 11. In addition, the injection / recovery port 16 may be provided with a closed structure such as a rotary cock 17 having a fit.
分離槽１１のうち、内底面１１ａをなし、注入／回収口１６と連通する部分は、注入／回収口１６側に向かうに従って次第に幅（径）が小さくなるテーパ形状をなしている。分離槽１１の内底面１１ａがテーパ形状をなすことにより、分離槽１１の内のナノカーボンの分散液３０を、円滑に回収することができる。 A part of the separation tank 11 which constitutes the inner bottom surface 11a and communicates with the injection / recovery port 16 has a tapered shape in which the width (diameter) gradually decreases toward the injection / recovery port 16 side. By forming the inner bottom surface 11a of the separation tank 11 in a tapered shape, the dispersion 30 of nanocarbon in the separation tank 11 can be smoothly recovered.
分離槽１１の底部の注入／回収口１６を介して、例えば、ペリスタポンプ等を用いて静かにナノカーボンの分散液３０の注入、および、回収を行うことにより、注入／回収時に、液面の変化に合わせて注入／回収口を移動させる必要がなく、分離槽１１内部の液相界面を乱すことなく、注入／回収操作を行うことができる。また、分離槽１１を高容量化した場合に、長い注入／回収ノズルを用意する必要もなく、非常に合理的である。 For example, by injecting and recovering the nanocarbon dispersion liquid 30 gently using a peristaltic pump or the like via the injection / recovery port 16 at the bottom of the separation tank 11, the change in liquid level at the time of injection / recovery It is not necessary to move the injection / recovery port in accordance with the above, and the injection / recovery operation can be performed without disturbing the liquid phase interface inside the separation tank 11. In addition, when the capacity of the separation tank 11 is increased, it is very rational without the need to prepare a long injection / recovery nozzle.
本実施形態のナノカーボン分離装置２００では、第１の電極２０２が陰極、第２の電極２０３が陽極である場合を例示したが、本実施形態のナノカーボン分離装置２００はこれに限定されない。本実施形態のナノカーボン分離装置２００にあっては、第１の電極２０２が陽極、第２の電極２０３が陰極であってもよい。 Although the case where the 1st electrode 202 is a cathode and the 2nd electrode 203 is an anode was illustrated in the nanocarbon separation apparatus 200 of this embodiment, the nanocarbon separation apparatus 200 of this embodiment is not limited to this. In the nanocarbon separation apparatus 200 of the present embodiment, the first electrode 202 may be an anode, and the second electrode 203 may be a cathode.
　本実施形態のナノカーボン分離装置２００によれば、第１の電極２０２を、多孔質構造物１０１の最上層を構成する粒子１０２と、粒子１０２の表面に形成された金属膜１０３を有する電極粒子１１０からなるものとし、第２の電極２０３を、多孔質構造物１０１の最下層を構成する粒子１０２と、粒子１０２の表面に形成された金属膜１０３を有する電極粒子１１０からなるものとすることにより、分離槽１１内において、第１の電極２０２および第２の電極２０３を設けるための空間を確保する必要がない。また、本実施形態のナノカーボン分離装置２００によれば、第２の電極２０３を電極粒子１１０からなるものとし、多孔質構造物１０１を分離槽１１内に充填された複数の粒子１０２からなるものとすることにより、粒子１０２と電極粒子１１０が自由に動くことができるため、注入／回収口１６を介して、分離槽１１内に注入／回収口ノズルを挿入した場合に、粒子１０２と電極粒子１１０が注入／回収口ノズルを邪魔することがない。そのため、注入／回収口１６を介して、分離槽１１に対するナノカーボンの分散液３０の注入、および、回収をスムーズに行うことができる。また、本実施形態のナノカーボン分離装置２００によれば、第１の電極２０２と第２の電極２０３の間に、分離槽１１内に充填された複数の粒子１０２からなる多孔質構造物１０１を設けることにより、例えば、後述するナノカーボンの分離方法を実施する、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程において、分離槽１１内にて、ナノカーボンの分散液３０に水平方向の流れが生じるのを抑制することができる。したがって、金属型ナノカーボンと半導体型ナノカーボンを迅速に分離することができる。よって、純度が高い金属型ナノカーボンと半導体型ナノカーボンを得ることができる。 According to the nanocarbon separation apparatus 200 of the present embodiment, the first electrode 202 includes the particles 102 constituting the uppermost layer of the porous structure 101, and the electrode particles having the metal film 103 formed on the surface of the particles 102. The second electrode 203 is composed of a particle 102 constituting the lowermost layer of the porous structure 101 and an electrode particle 110 having a metal film 103 formed on the surface of the particle 102. Thus, it is not necessary to secure a space for providing the first electrode 202 and the second electrode 203 in the separation tank 11. Further, according to the nanocarbon separation apparatus 200 of the present embodiment, the second electrode 203 is made of the electrode particles 110, and the porous structure 101 is made of a plurality of particles 102 filled in the separation tank 11. The particle 102 and the electrode particle 110 can move freely by setting the particle 102 and the electrode particle when the injection / recovery nozzle is inserted into the separation tank 11 through the injection / recovery port 16. 110 does not disturb the inlet / recovery nozzle. Therefore, the injection and recovery of the nanocarbon dispersion liquid 30 into the separation tank 11 can be smoothly performed via the injection / recovery port 16. Further, according to the nanocarbon separation apparatus 200 of the present embodiment, the porous structure 101 formed of the plurality of particles 102 filled in the separation tank 11 is formed between the first electrode 202 and the second electrode 203. In the step of separating metallic nanocarbon and semiconducting nanocarbon contained in dispersion liquid of nanocarbon, for example, implementing the separation method of nanocarbon described later, by providing the nanocarbon in separation tank 11 It is possible to suppress the occurrence of horizontal flow in the dispersion liquid 30 of Therefore, metallic nanocarbon and semiconducting nanocarbon can be separated rapidly. Therefore, metal nanocarbon and semiconductor nanocarbon with high purity can be obtained.
（ナノカーボンの分離方法）
　図７を用いて、ナノカーボン分離装置２００を用いた、ナノカーボンの分離方法を説明するとともに、ナノカーボン分離装置２００の作用を説明する。 (Separation method of nano carbon)
While demonstrating the separation | isolation method of nanocarbon using the nanocarbon separation apparatus 200 using FIG. 7, the effect | action of the nanocarbon separation apparatus 200 is demonstrated.
　本実施形態のナノカーボンの分離方法は、第１の実施形態と同様に、分離槽１１にナノカーボンの分散液３０を注入する工程（注入工程）と、第１の電極２０２と第２の電極２０３に直流電圧を印加し、ナノカーボンの分散液３０に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程（分離工程）と、を有する。
　注入工程にて、分離槽１１にナノカーボンの分散液３０を注入することにより、ナノカーボンの分散液３０に第１の電極２０２と第２の電極２０３が接する。本実施形態では、ナノカーボンの分散液３０に第１の電極２０２と第２の電極２０３を浸漬した。 Similar to the first embodiment, the method of separating nanocarbon according to the present embodiment includes the step of injecting the dispersion 30 of nanocarbon into the separation tank 11 (injection step), and the first electrode 202 and the second electrode. It has a process (separation process) which applies a direct current voltage to 203 and separates metallic nanocarbon and semiconducting nanocarbon contained in the dispersion liquid 30 of nanocarbon.
In the injection step, the nanocarbon dispersion liquid 30 is injected into the separation tank 11 so that the first electrode 202 and the second electrode 203 are in contact with the nanocarbon dispersion liquid 30. In the present embodiment, the first electrode 202 and the second electrode 203 are immersed in the nanocarbon dispersion liquid 30.
　本実施形態では、分離槽１１内に複数の粒子１０２を充填して多孔質構造物１０１を形成し、分離槽１１内を複数の領域に区画する。これにより、分離工程において、電気泳動法によって、分離槽１１内にて、単層カーボンナノチューブ分散液を相分離する際、単層カーボンナノチューブ分散液に水平方向の流れが生じるのを抑制することができる。その結果、内径が大きな分離槽１１を用いた場合にも、迅速に、多孔質構造物１０１における第１の電極２０２側の領域に分散液相Ａを含む領域Ａを形成し、多孔質構造物１４における第２の電極２０３側の領域に分散液相Ｂを含む領域Ｂを形成して、単層カーボンナノチューブ分散液を分散液相Ａと分散液相Ｂに相分離することができる。 In the present embodiment, a plurality of particles 102 are filled in the separation tank 11 to form the porous structure 101, and the inside of the separation tank 11 is partitioned into a plurality of regions. Thereby, in the separation step, when the single-walled carbon nanotube dispersion liquid is phase-separated in the separation tank 11 by the electrophoresis method, generation of a horizontal flow in the single-walled carbon nanotube dispersion liquid is suppressed it can. As a result, even when the separation tank 11 having a large inner diameter is used, the region A including the dispersion liquid phase A is rapidly formed in the region on the first electrode 202 side of the porous structure 101, and the porous structure A single-walled carbon nanotube dispersion liquid can be phase-separated into the dispersion liquid phase A and the dispersion liquid phase B by forming the area B containing the dispersion liquid phase B in the area on the second electrode 203 side in.
　本実施形態のナノカーボン分離装置２００を用いたナノカーボンの分離方法によれば、第１の電極２０２と第２の電極２０３の間に、複数の粒子１０２の集合体からなる多孔質構造物１０１を設けることにより、分離槽１１内にて、単層カーボンナノチューブ分散液に水平方向の流れが生じるのを抑制することができる。この結果、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを迅速に分離することができる。よって、純度が高い金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを得ることができる。 According to the nanocarbon separation method using the nanocarbon separation apparatus 200 of the present embodiment, the porous structure 101 formed of an aggregate of the plurality of particles 102 between the first electrode 202 and the second electrode 203. By providing the single-walled carbon nanotube dispersion liquid in the separation tank 11, it is possible to suppress the occurrence of the flow in the horizontal direction. As a result, metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes can be separated rapidly. Thus, metal single-walled carbon nanotubes and semiconductor single-walled carbon nanotubes with high purity can be obtained.
　なお、本実施形態のナノカーボンの分離方法では、単層カーボンナノチューブの混合物を、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離する場合を例示したが、本実施形態のナノカーボンの分離方法はこれに限定されない。本実施形態のナノカーボンの分離方法は、分離槽１１内にて、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離した後、目的の性質を有する単層カーボンナノチューブのみを回収する、単層カーボンナノチューブの精製方法として行ってもよい。 In the method of separating nanocarbons of the present embodiment, the case of separating a mixture of single-walled carbon nanotubes into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes has been exemplified. The separation method is not limited to this. In the method for separating nanocarbons of the present embodiment, metal single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes are separated in the separation tank 11, and then only single-walled carbon nanotubes having desired properties are recovered. You may carry out as a purification method of a single-walled carbon nanotube.
（ナノカーボンの回収方法）
　本実施形態のナノカーボンの回収方法は、本実施形態のナノカーボン分離装置２００を用いたナノカーボンの分離方法による分離操作が終了した後、多孔質構造物１０１を、金属型単層カーボンナノチューブを多く含む領域Ａと半導体型単層カーボンナノチューブを多く含む領域Ｂとに分割し、領域Ａから金属型単層カーボンナノチューブを回収し、領域Ｂから半導体型単層カーボンナノチューブを回収する。 (Recovery method of nano carbon)
In the method for recovering nanocarbon of the present embodiment, after the separation operation by the method for separating nanocarbon using the nanocarbon separation device 200 of the present embodiment is completed, the porous structure 101 is replaced by metal single-walled carbon nanotubes. It is divided into a region A containing a large amount and a region B containing a large amount of semiconducting single-walled carbon nanotubes, metal single-walled carbon nanotubes are recovered from the region A, and semiconducting single-walled carbon nanotubes are collected from the region B.
　回収方法は、特に限定されず、分散液相Ａと分散液相Ｂが拡散混合しない方法であればいかなる方法であってもよい。
　本実施形態のナノカーボンの回収方法では、回収方法としては、例えば、第１の実施形態と同様の方法が用いられる。 The recovery method is not particularly limited, and any method may be used as long as the dispersion liquid phase A and the dispersion liquid phase B do not diffuse and mix.
In the nanocarbon recovery method of the present embodiment, as the recovery method, for example, the same method as in the first embodiment is used.
　また、第１の実施形態と同様にして、回収した分散液を、再び、分離槽１１に収容し、電気泳動法により、単層カーボンナノチューブ分散液に含まれる金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブを分離する操作を繰り返し実施してもよい。 Further, in the same manner as in the first embodiment, the recovered dispersion is again accommodated in the separation tank 11, and the single-walled carbon nanotube dispersion and the semiconductor single-walled carbon nanotube contained in the single-walled carbon nanotube dispersion by electrophoresis. The operation of separating single-walled carbon nanotubes may be repeated.
　回収した分散液の分離効率は、第１の実施形態と同様にして、評価することができる。 The separation efficiency of the recovered dispersion can be evaluated in the same manner as in the first embodiment.
　本実施形態のナノカーボンの回収方法によれば、本実施形態のナノカーボンの分離方法による分離操作が終了した後、多孔質構造物１０１の領域Ａから金属型ナノカーボンを効率的に回収することができ、多孔質構造物１０１の領域Ｂから半導体型ナノカーボンを効率的に回収することができる。 According to the method of recovering nano carbon of the present embodiment, after the separation operation by the method of separating nano carbon of the present embodiment is completed, metal nanocarbon is efficiently recovered from the region A of the porous structure 101. As a result, the semiconductor nanocarbon can be efficiently recovered from the region B of the porous structure 101.
［第４の実施形態］
（ナノカーボンの分離方法）
図８を用いて、ナノカーボン分離装置１０を用いた、ナノカーボンの分離方法を説明する。
まず、水と、非イオン性界面活性剤を溶解した水溶液に単層カーボンナノチューブの混合物を分散させた単層カーボンナノチューブ分散液と、非イオン性界面活性剤の含有量が２ｗｔ％の水溶液を調製する。
次いで、例えば、分離槽１１の下端に設けられた注入／回収口（図示略）から分離槽１１内へ、ペリスタポンプ等を用いて水を静かに注入する。
次いで、同様に、分離槽１１内へ、単層カーボンナノチューブ分散液を注入する。
次いで、同様に、分離槽１１内へ、非イオン性界面活性剤の含有量が２ｗｔ％の水溶液を注入する。
これにより、図８に示すように、第１の電極１２に接する領域は水、第２の電極１３に接する領域は２ｗｔ％の水溶液、中間の領域は単層カーボンナノチューブ分散液である、３層の溶液の積層構造を形成した。
このとき、第１の電極１２は水のみに接し、第２の電極１３は２ｗｔ％の水溶液のみに接している。また、第１の電極１２および第２の電極１３は単層カーボンナノチューブ分散液に接していない。 Fourth Embodiment
(Separation method of nano carbon)
A separation method of nanocarbon using the nanocarbon separation device 10 will be described with reference to FIG.
First, a single-walled carbon nanotube dispersion in which a mixture of single-walled carbon nanotubes is dispersed in an aqueous solution in which water and a nonionic surfactant are dissolved, and an aqueous solution containing 2 wt% of a nonionic surfactant are prepared. Do.
Next, for example, water is gently injected into the separation tank 11 from an injection / recovery port (not shown) provided at the lower end of the separation tank 11 using a perister pump or the like.
Then, similarly, the single-walled carbon nanotube dispersion liquid is injected into the separation tank 11.
Then, similarly, an aqueous solution having a nonionic surfactant content of 2 wt% is injected into the separation tank 11.
Thereby, as shown in FIG. 8, the region in contact with the first electrode 12 is water, the region in contact with the second electrode 13 is a 2 wt% aqueous solution, and the middle region is a single-walled carbon nanotube dispersion. Form a layered structure of the solution.
At this time, the first electrode 12 is in contact with only water, and the second electrode 13 is in contact with only a 2 wt% aqueous solution. Further, the first electrode 12 and the second electrode 13 are not in contact with the single-walled carbon nanotube dispersion liquid.
　以下、第１の実施形態と同様にして、単層カーボンナノチューブ分散液に含まれる単層カーボンナノチューブの混合物を、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離する。 Hereinafter, in the same manner as in the first embodiment, the mixture of single-walled carbon nanotubes contained in the single-walled carbon nanotube dispersion liquid is separated into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes.
本実施形態のナノカーボンの分離方法は、上述の第１～第３の実施形態にも適用できる。 The method for separating nanocarbons of the present embodiment can also be applied to the first to third embodiments described above.
　以上、単層カーボンナノチューブの混合物を、金属型単層カーボンナノチューブと半導体型単層カーボンナノチューブに分離する場合に適用することができる実施形態を説明したが、多層カーボンナノチューブの混合物、二層カーボンナノチューブの混合物、グラフェンの混合物等を分離する場合にも、本発明を適用することができる。 Although the embodiments applicable to the case of separating a mixture of single-walled carbon nanotubes into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes have been described above, a mixture of multi-walled carbon nanotubes, double-walled carbon nanotubes The present invention can also be applied to the case of separating mixtures of graphene, mixtures of graphene, and the like.
本発明のナノカーボン分離装置は、ナノカーボンの混合物の分離において、分離に要する時間を短縮することができる。 The nanocarbon separation apparatus of the present invention can reduce the time required for separation in the separation of a mixture of nanocarbons.
１０，１００，２００・・・ナノカーボン分離装置、
１１・・・分離槽、
１２，２０２・・・第１の電極、
１３，２０３・・・第２の電極、
１４，１０１・・・多孔質構造物、
３０・・・ナノカーボンの分散液、
５０・・・切断刃、
１０２・・・粒子、
１０３・・・電極粒子、
１１０・・・電極粒子、
２０４，２０５・・・導線。 10, 100, 200 ... nano carbon separation device,
11 ... separation tank,
12, 202 ... first electrode,
13, 203 ··· second electrode,
14,101 ... porous structure,
30 · · · dispersion of nano carbon,
50 ... cutting blade,
102 ... particle,
103 ... electrode particles,
110 ... electrode particles,
204, 205 ... lead wire.

Claims (7)

  1. ナノカーボンを含む分散液を収容する分離槽と、
    前記分離槽内の上部に設けられた第１の電極と、
    前記分離槽内の下部に設けられた第２の電極と、
    前記分離槽内にて前記第１の電極と前記第２の電極の間に設けられた多孔質構造物と、を備えることを特徴とするナノカーボン分離装置。     A separation vessel containing a dispersion containing nanocarbon,
    A first electrode provided at an upper portion in the separation tank;
    A second electrode provided at a lower portion in the separation tank,
    A nanocarbon separation device comprising a porous structure provided between the first electrode and the second electrode in the separation tank.
  2. 　前記多孔質構造物は、スポンジからなることを特徴とする請求項１に記載のナノカーボン分離装置。 The nanocarbon separation device according to claim 1, wherein the porous structure is a sponge.
  3. 　前記多孔質構造物は、複数の粒子の集合体であることを特徴とする請求項１に記載のナノカーボン分離装置。 The nanocarbon separation device according to claim 1, wherein the porous structure is an aggregate of a plurality of particles.
  4. 　前記第１の電極および前記第２の電極は、前記粒子と該粒子の表面に形成された金属膜を有する電極粒子からなることを特徴とする請求項３に記載のナノカーボン分離装置。 The nanocarbon separation device according to claim 3, wherein the first electrode and the second electrode are composed of electrode particles having the particles and a metal film formed on the surfaces of the particles.
  5. 　請求項１～４のいずれか１項に記載のナノカーボン分離装置を用いたナノカーボンの分離方法であって、
    　前記分離槽にナノカーボンを含む分散液を注入する工程と、
    前記第１の電極と前記第２の電極に直流電圧を印加し、前記分散液に含まれる金属型ナノカーボンと半導体型ナノカーボンを分離する工程と、を有することを特徴とするナノカーボンの分離方法。     A method for separating nanocarbons using the nanocarbon separation device according to any one of claims 1 to 4, comprising:
    Injecting a dispersion containing nanocarbon into the separation tank;
    A step of applying a DC voltage to the first electrode and the second electrode to separate the metal nanocarbon and the semiconductor nanocarbon contained in the dispersion; Method.
  6. 前記分散液を注入する工程において、前記分離槽の下部から順に、界面活性剤の水溶液からなる層、前記分散液からなる層、水からなる層を形成し、前記第１の電極を前記水からなる層のみに接触させ、前記第２の電極を前記水溶液からなる層のみに接触させることを特徴とするナノカーボンの分離方法。 In the step of injecting the dispersion, a layer comprising an aqueous solution of a surfactant, a layer comprising the dispersion, and a layer comprising water are sequentially formed from the lower part of the separation tank, and the first electrode is formed of the water A method of separating nanocarbon, comprising: contacting only the layer; and contacting the second electrode only with the layer consisting of the aqueous solution.
  7. 　請求項１～４のいずれか１項に記載のナノカーボン分離装置を用いたナノカーボンの回収方法であって、
    前記ナノカーボン分離装置による分離操作が終了した後、前記多孔質構造物を、金属型ナノカーボンを多く含む領域Ａと半導体型ナノカーボンを多く含む領域Ｂとに分割し、前記領域Ａから前記金属型ナノカーボンを回収し、前記領域Ｂから前記半導体型ナノカーボンを回収することを特徴とするナノカーボンの回収方法。     A method of recovering nanocarbon using the nanocarbon separation device according to any one of claims 1 to 4, comprising:
    After the separation operation by the nanocarbon separation device is completed, the porous structure is divided into a region A containing a large amount of metallic nanocarbon and a region B containing a large amount of semiconducting nanocarbon, and the metal from the region A Type nanocarbon is recovered, and the semiconductor type nanocarbon is recovered from the region B.
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